CN102812401B - Photocurable/thermosetting resin composition, dry film thereof and cured substance therefrom, and printed circuit board using same - Google Patents

Abstract

The disclosed photocurable/thermosetting resin composition, which can be developed by an alkaline aqueous solution, can form a cured film that has properties important for a solder resist for semiconductor packages, namely PCT and HAST reliability and resistance to immersion gold plating and thermal shock. Said photocurable/thermosetting resin composition contains: (A) a carboxyl-containing resin (but not a carboxyl-containing resin made from an epoxy resin); (B) a photopolymerization initiator; and (C) a naphthalene-ring-containing epoxy resin. Preferably, the carboxyl-containing resin does not contain any hydroxyl groups and does contain a photosensitive group. Also disclosed is a printed circuit board on which the disclosed photocurable/thermosetting resin composition or a dry film thereof is used to form a cured film such as a solder resist.

Description

Light solidifying/heat solidifying resin composition, its dry film and solidfied material and use it Printed circuit board (PCB)

Technical field

The present invention relates to can be by the light solidifying/heat solidifying resin composition of aqueous alkali development, especially by purple Outer line exposing or laser explosure carry out solder resist composition, its dry film and the solidfied material of photocuring and with using them The printed circuit board (PCB) of the cured film of formation.

Background technology

At present, the solder resist of the industrial printed circuit board (PCB) of a part of civilian printed circuit board (PCB) and the overwhelming majority is from high-precision Degree, from the viewpoint of high density, using being formed image by being developed after ultraviolet exposure, with heat and/or light irradiation Finally solidified（It is primary curing）Liquid developable solder flux, for the consideration to environmental problem, made using aqueous alkali Photic solder resist for the alkali developable of developer solution becomes main flow, and it is largely used to the manufacture of actual printed circuit board (PCB).In addition, Corresponding to the densification of the printed circuit board (PCB) associated with the frivolous miniaturization of electronic equipment in recent years, also require that solder resist has There are operability, high performance.

However, the photic solder resist of existing alkali developable there is a problem in durability.That is, with traditional heat cure Type, the solder resist of solvent development type are compared, and alkali resistance, resistance to water, heat resistance etc. are poor.It is believed that this be due to：Alkali developable In order to be able to carry out alkali development, the material with hydrophilic radical becomes main component, liquid, water, vapor etc. to photic solder resist It is readily permeable, so that the adaptation of chemical proofing reduction, welding resistance epithelium and copper is reduced.As a result, as chemically-resistant medicine The alkali resistance of moral character is weak, especially in BGA（Ball Grid Array, BGA）、CSP（Chip Size Package, chip Sized package）Etc. specially requiring the PCT patience that should also be referred to as humidity resistance in semiconductor packages（Pres sure Cooker Test Resistance, pressure cooker testing patience）, but present situation is that ~ more than ten can only be adhered to a few houres under such critical conditions Hour or so.In addition, the HAST tests under humidified condition in the state of applied voltage（High Accelerated Stress Test, height accelerated life test）In, in most cases, a few houres just confirm bad caused by migration by occurring.

In addition, in recent years, to surface-pasted transformation, the use of the lead-free solder for also having the adjoint consideration to environmental problem Deng, exist to encapsulation apply temperature become very high tendency.Therewith, the arrival temperature for encapsulating inside and outside significantly increases, and passes The liquid photosensitive solder resist of system exist film deteriorate because of thermal history or characteristic change, it is peeling-off or as previously mentioned PCT, HAST patience be deteriorated problem, need to improve it.

On the other hand, generally using containing carboxy resin used in existing solder resist is spread out by the modified of epoxy resin The epoxy acrylate modified resin that life is obtained.For example, Japanese Unexamined Patent Application 61-243869 publication（Patent document 1）Middle report The solder mask composition being made up of photoresist, Photoepolymerizationinitiater initiater, diluent and epoxide, wherein described photosensitive Property resin is obtained to novolak type epoxy compounds with unsaturated monacid product addition acid anhydrides.In addition, Japanese Unexamined Patent 3-250012 publication（Patent document 2）In disclose by groups such as photoresist, Photoepolymerizationinitiater initiater, organic solvents Into solder mask composition, wherein the photoresist to make salicylide and monohydric phenol the reaction of product and epichlorohydrin and The epoxy resin addition for obtaining（Methyl）Acrylic acid is simultaneously further obtained with polybasic carboxylic acid or its anhydride reaction.

Above-mentioned such epoxy acrylate modified resin remaining has a large amount of hydroxyls from epoxy acrylate, originally There is the problem of poor water resistance.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Application 61-243869 publication

Patent document 2：Japanese Unexamined Patent Publication 3-250012 publication

The content of the invention

Problems to be solved by the invention

The present invention be in view of aforementioned such problem of the prior art and make, its main purpose is to provide a kind of light Curability hot curing resin composition, its be formed as the semiconductor-sealing-purpose solder mask required by the thermal history under high temperature and With important PCT patience, HAST patience, the gold-plated property of chemically-resistant, cold-resistant thermal impact cured film.

Further, the present invention also aims to provide by using such light solidifying/heat solidifying resin composition The dry film and solidfied material of the above-mentioned such all excellents for obtaining and solder mask etc. is formed by the dry film, solidfied material solidify The printed circuit board (PCB) of epithelium.

For solution to problem

In order to reach object defined above, according to the present invention, there is provided the photo-curable thermosetting that a kind of energy is developed by aqueous alkali The property changed resin combination, it is characterised in that it contains containing carboxy resin（Wherein exclude with epoxy resin as initiation material containing carboxylic Base resin）, Photoepolymerizationinitiater initiater and epoxy resin containing naphthalene nucleus.

It is above-mentioned that preferably there is photonasty group containing carboxy resin.

Further, according to the present invention, there is provided aforementioned light solidifying/heat solidifying resin composition is coated with a carrier film simultaneously The dry film of Photosetting and thermosetting obtained from drying and, by aforementioned light solidifying/heat solidifying resin composition or dry film Carry out photocuring, preferably with solidfied material obtained from the light source into pattern-like photocuring of wavelength 350nm ~ 410nm.

Furthermore, according to the present invention, a kind of printed circuit board (PCB) also being provided, it has cured film, and the cured film passes through To aforementioned light solidifying/heat solidifying resin composition or dry film irradiation active energy beam, preferred ultraviolet direct description from And be light-cured into after pattern-like, carry out heat cure and obtain.

The effect of invention

The light solidifying/heat solidifying resin composition of the present invention is due to as the composition that can be developed by aqueous alkali, making It is with containing carboxy resin and in combination containing epoxy resin containing naphthalene nucleus with epoxy resin as initiation material therefore not only solid Change the obdurability of film, heat resistance to improve, and film is with low uncertainty in the physical property after thermal history and when crossing solidification.Further, make us Surprisingly it has been found that, even if heat curing temperature is relatively low still to have good curability, even and if at relatively high temperatures applying heat is gone through Journey, can also maintain good characteristic and physical property will not change.Therefore, by using the Photosetting and thermosetting resin of the present invention Composition, can form with as PCT patience important for semiconductor-sealing-purpose solder mask, HAST patience, chemically-resistant plating The cured film of Jin Xing, excellent heat resistance.

Specific embodiment

As it was previously stated, the light solidifying/heat solidifying resin composition of the present invention is characterised by containing not with epoxy resin It is initiation material containing carboxy resin, Photoepolymerizationinitiater initiater and epoxy resin containing naphthalene nucleus.

As above-mentioned containing carboxy resin, as long as not can use now containing carboxy resin with epoxy resin as initiation material Have known various containing carboxy resin, wherein, the photoresist containing carboxyl with ethene unsaturated double-bond is from light in molecule It is preferred from the point of view of curability, resistance to developability aspect.Then, the unsaturated double-bond is preferably derived from acrylic or methacrylic acid Or their derivative.Additionally, only using the not when containing carboxy resin with ethene unsaturated double-bond, in order that composition For photo-curable, need to be applied in combination in molecule as described later the compound with more than 1 ethene unsaturated group（Sense Photosensitiveness monomer）.

As the specific example containing carboxy resin that can be used for the present invention, the such compound being preferably exemplified below （Can be any one in oligomer and polymer）.

（1）Make（Methyl）The monocarboxylic acid containing unsaturated group such as acrylic acid and bisphenol-A, Bisphenol F, bisphenol S, phenolic varnish type Have in the molecule of condensation product of condensation product, dihydroxy naphthlene and aldehydes of phenolic resin, poly(4-hydroxystyrene), naphthols and aldehydes etc. 1 There is product obtained from the reaction of the epoxyalkane such as compound and oxirane, the expoxy propane of more than 2 phenolic hydroxyl group to enter Row reaction, and make the multi-anhydrides such as maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic anhydride With photoresist containing carboxyl obtained from gained reaction.

（2）The monocarboxylic acid containing unsaturated group is made with the compound and carbonic acid that make that there is more than 2 phenolic hydroxyl group in 1 molecule Product obtained from the reaction of the cyclic carbonate compounds such as ethyl, propylene carbonate is reacted, and makes multi-anhydride With photoresist containing carboxyl obtained from gained reaction.

（3）Make the end of polyurethane resin and the carboxylic polyurethane resin in end of anhydride reaction, the poly- ammonia Ester resin is different by aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series two The diisocyanate cpds such as cyanate and polycarbonate-based polyalcohol, polyethers system polyalcohol, polyester-based polyols, polyolefin Polyalcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adducts glycol, the chemical combination with phenolic hydroxyl group and alcohol hydroxyl group Obtained from the sudden reaction of the diol compounds such as thing.

（4）By compounds containing carboxylic diol and two such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acids Hydroxy alkyl is added in synthesis containing carboxyl polyurethane resin obtained from the sudden reaction of alcoholic compound（Methyl）Acrylate There is 1 hydroxyl and more than 1 in equimolecular（Methyl）The compound of acryloyl group, by end（Methyl）It is acrylated and obtain Polyurethane resin containing carboxyl.

（5）Contain obtained from by sudden reaction of the diisocyanate with compound containing carboxylic diol and diol compound The reaction with same mole of IPDI and pentaerythritol triacrylate is added in the synthesis of carboxyl polyurethane resin There is 1 NCO and more than 1 in thing equimolecular（Methyl）The compound of acryloyl group, by end（Methyl）Acryloyl Polyurethane resin containing carboxyl obtained from change.

（6）Pass through（Methyl）The unsaturated carboxylic acids such as acrylic acid and styrene, AMS,（Methyl）Acrylic acid lower Contain carboxy resin obtained from the copolymer compounds containing unsaturated group such as Arrcostab, isobutene.

（7）The dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid are made with multifunctional oxa- ring fourth as described later Alkane resin reaction, and in primary hydroxyl addition phthalate anhydride, tetrabydrophthalic anhydride, the hexahydrophthalic acid to being generated Containing further addition on carboxyl polyester resin obtained from the dibasic acid anhydrides such as acid anhydride（Methyl）Glycidyl acrylate,（Methyl）Third There is 1 epoxy radicals and more than 1 in 1 molecules such as olefin(e) acid Alpha-Methyl ethylene oxidic ester（Methyl）The compound of acryloyl group is formed Photoresist containing carboxyl.

（8）To aforementioned（1)~（7）The molecule of addition containing carboxy resin 1 in have cyclic ether group and（Methyl）Acryloyl group Photoresist containing carboxyl obtained from compound.

Additionally, in the description,（Methyl）Acrylate is to be referred to as acrylate, methacrylate and theirs is mixed The term of compound, it is other below to be similar to expression similarly.

Used in the present invention containing carboxy resin due to epoxy resin not being used as into initiation material, therefore contain with halide The considerably less feature of amount.The chloride ion impurities content containing carboxy resin used in the present invention be 0 ~ 100ppm, more preferably 0 ~ 50ppm, more preferably 0 ~ 30ppm.

In addition, the not resin with hydroxyl can be readily derived containing carboxy resin used in the present invention.Although known Generally the presence of hydroxyl is also with excellent features such as the adaptation raisings brought by hydrogen bond, but can significantly reduce moisture-proof.With Of the invention containing carboxyl tree of the lower explanation with the epoxy acrylate system modified resin used in conventional solder resist by contrast The excellent part of fat.

Not chloride phenol resol resins can be readily derived.Obtained by carrying out epoxyalkane modified to it The phenolic resin moiety propylene acidifying arrived and importing acid anhydrides, so as to double bond equivalent 300 ~ 550,40 ~ 120mgKOH/ of acid number is obtained The scope of g and in theory not with hydroxyl resin.

On the other hand, if by the epoxy radicals of the epoxy resin synthesized by similar phenol resol resins whole propylene It is acidified, acid anhydrides is imported to all hydroxyls, then double bond equivalent is that 400 ~ 500 and acid number can become very large, even if becoming in exposure The film with resistance to developability cannot be also obtained afterwards.Further, the poor water resistance because acid number is high, hence it is evident that reduction insulating reliability, PCT patience.That is, from being derived by similar phenol novolak type epoxy resin in the epoxy acrylate system modified resin that obtains It is extremely difficult that hydroxyl is removed completely.

Thus, existing epoxy acrylate system modified resin inevitably has hydroxyl, but the presence of hydroxyl is not only Have an impact in absorptive angle, epoxy resin is also had an impact with the reactivity of acid.I.e., although known hydroxyl can promote acid With the reaction of epoxy radicals, but be contemplated that：The presence of hydroxyl facilitation effect before solidfied material forms gel is high, and in reactant It is that its facilitation effect is little after gelation.I.e., it is believed that for the acid in the system that there is great amount of hydroxy group and epoxy radicals Reaction, it is that the terminal for reacting is slack-off that reaction starts to become early cost.With regard to reaction relatively it is early start this point for, from composition can It is undesirable with the time, from development longevity of the solvent to development is dried, further as in earlier stage Form gel and cause until reaction completes to need prolonged high temperature.Because the composition of the present invention is in the shape that there is no hydroxyl React under state, it can be said that reaction is reacted leniently.It is believed that life-span length of the result to development, and then instead Should easily terminate.It is believed that result obtains excellent reliability.It is bright during the epoxy resin containing naphthalene nucleus that the phenomenon is stated after use Explict occurrence.It is believed that this is to receive because of the naphthalene nucleus containing naphthalene nucleus epoxy resin that melt viscosity is relatively low for planar structure, reactivity Higher impact.

In addition, polyurethane resin can also be easily synthesized not by making hydroxyl corresponding with the equivalent of NCO Resin with hydroxyl.Preferred resin is by by phosgene not being used as the isocyanate compound of initiation material, do not use table halogen For the Material synthesis of alcohol chloride ion impurities 0 ~ 30ppm of amount containing carboxy resin, more preferably not having hydroxyl in theory The resin that the mode of base synthesizes.

From such angle, can particularly preferably use previously as shown in specific example containing carboxy resin （1）~（5）.

In addition, make it is indicated before by with obtained from the copolymer compound containing unsaturated group containing carboxy resin（6） With as in 1 molecule have cyclic ether group and（Methyl）The methacrylic acid 3,4- epoxycyclohexyl first of the compound of acryloyl group Photoresist containing carboxyl is due to having used alicyclic epoxy thing obtained from ester reaction, therefore chloride ion impurities are less, Can suitably use.

On the other hand, make containing carboxy resin（6）With as in 1 molecule have cyclic ether group and（Methyl）The change of acryloyl group Resin obtained from the GMA reaction of compound, make containing carboxy resin（6）With as containing unsaturated group Compound GMA copolymerization obtained from resin there is many anxieties of chloride ion impurities quantitative change.In addition, During the synthesis of polyurethane resin, it is also possible to using epoxy acrylate modified feedstock as diol compound.Although chlorine can be mixed into Ionic impurity, but can use from the angle that can control chloride ion impurities amount.

Above-mentioned such carboxy resin that contains is due in trunk polymer（backbone polymer）Side chain have it is multiple Free carboxyl, therefore can be developed using aqueous alkali.

In addition, the above-mentioned acid number containing carboxy resin is preferably the scope of 40 ~ 150mgKOH/g, more preferably 40 ~ The scope of 130mgKOH/g.When acid number containing carboxy resin is less than 40mgKOH/g, alkali development can be difficult to, on the other hand, be exceeded During 150mgKOH/g, it may occur that by the dissolving of exposure portion caused by developer solution, therefore, line can become thinner than required, have When exposure portion and unexposed portion can indistinction be dissolved by the developing stripping, it is difficult to describe normal corrosion-resisting pattern.

In addition, the above-mentioned weight average molecular weight containing carboxy resin is different according to resin matrix, generally 2000 ~ 150000, Further the scope 5000 ~ 100000 is preferred.When weight average molecular weight is less than 2000, sometimes non-adhesion behavior is deteriorated, sometimes The moisture-proof of the film after exposure is poor, and film decrement occurs during development, and resolution ratio is significantly deteriorated.On the other hand, weight average molecular weight surpasses When 150000, sometimes developability significantly deteriorates, and sometimes storage stability is deteriorated.

Such compounding amount containing carboxy resin is 20 ~ 60 mass % in all compositions, preferably 30 ~ 50 mass %. During less than above range, coating strength can be reduced, and it is not preferable.When on the other hand, more than above range, viscosity is uprised, or is applied Cloth etc. can be reduced, and it is not preferable.

In resin combination composition Photocurable resin composition or Photosetting and thermosetting resin group by the present invention During compound, Photoepolymerizationinitiater initiater can be compounded.As preferred initiator, it is possible to use selected from the oxime ester system with oxime ester base In Photoepolymerizationinitiater initiater, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, the group of acylphosphine oxide system Photoepolymerizationinitiater initiater composition 1 Plant the Photoepolymerizationinitiater initiater of the above.

For oxime ester system Photoepolymerizationinitiater initiater, as commercially available product, the CGI- of Ciba Japan K.K. manufactures can be included 325、IRGACURE（Registration mark）N-1919, NCI-831 of the manufacture of OXE01, IRGACURE OXE02, ADEKA company etc..Separately Outward, it is also possible to suitably using the Photoepolymerizationinitiater initiater in molecule with 2 oxime ester bases, specifically, can include following logical The oxime ester compound with carbazole structure shown in formula.

[chemical formula 1]

（In formula, X represents hydrogen atom, the alkyl of carbon number 1 ~ 17, the alkoxyl of carbon number 1 ~ 8, phenyl, by the alkane of carbon number 1 ~ 17 The phenyl that base, the alkoxyl of carbon number 1 ~ 8, amino, the alkylamino of the alkyl with carbon number 1 ~ 8 or dialkylamino instead of, by carbon What the alkyl of number 1 ~ 17, the alkoxyl of carbon number 1 ~ 8, amino, the alkylamino of the alkyl with carbon number 1 ~ 8 or dialkylamino instead of Naphthyl；Y, Z each represent hydrogen atom, the alkyl of carbon number 1 ~ 17, the alkoxyl of carbon number 1 ~ 8, halogen group, phenyl, by carbon number 1 ~ The benzene that 17 alkyl, the alkoxyl of carbon number 1 ~ 8, amino, the alkylamino of the alkyl with carbon number 1 ~ 8 or dialkylamino instead of Base, by the alkyl of carbon number 1 ~ 17, the alkoxyl of carbon number 1 ~ 8, amino, the alkylamino of the alkyl with carbon number 1 ~ 8 or dialkylamino The naphthyl that instead of, anthryl, pyridine radicals, benzofuranyl, benzothienyl；Ar represent singly-bound or carbon number 1 ~ 10 alkylidene, Ethenylidene, phenylene, biphenylene, sub- pyridine radicals, naphthylene, thiophene, anthrylene, sub- thienyl, furylidene, 2,5- pyrroles Cough up-diyl, 4,4 '-Stilbene-diyl, 4,2 '-styrene-diyl；N represents 0 or 1 integer.）

Especially in aforementioned formula, it is preferred that X, Y are respectively methyl or ethyl, Z is methyl or phenyl, and n is that 0, Ar is list Key or phenylene, naphthylene, thiophene or sub- thienyl.

Aforementioned containing carboxy resin relative to 100 mass parts, the compounding amount of such oxime ester system Photoepolymerizationinitiater initiater is preferably 0.01 ~ 5 mass parts.During less than 0.01 mass parts, photo-curable is not enough, and film is peeled off, and the film such as chemical proofing is special Property reduce.When on the other hand, more than 5 mass parts, aggravate in the light absorbs of film coated surface, there is inclining for deep curability reduction To.More preferably 0.5 ~ 3 mass parts.

As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically can include 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl]- 2- morpholinopropanones -1,2- benzyls -2- dimethylamino -1- (4- morphlinophenyls)-butane -1- ketone, 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone, N, N- dimethylamino acetophenones etc..As commercially available Product, can include IRGACURE 907, IRGACURE 369, IRGACURE 379 of Ciba Japan K.K. manufactures etc..

As acylphosphine oxide system Photoepolymerizationinitiater initiater, 2,4,6- trimethyl benzoyl diphenyl base oxygen can be specifically included Change phosphine, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides, double (2,6- Dimethoxybenzoyls) -2,4,4- front threes Base-amyl group phosphine oxide etc..As commercially available product, Lucirin TPO, the Ciba Japan K.K. of BASF AG's manufacture can be included IRGACURE 819 of manufacture etc..

It is aforementioned containing carboxy resin relative to 100 mass parts, these alpha-aminoacetophenone system Photoepolymerizationinitiater initiaters, acyl group oxidation The compounding amount of phosphine system Photoepolymerizationinitiater initiater is preferably 0.01 ~ 15 mass parts.During less than 0.01 mass parts, the light equally on copper is consolidated The coating characteristics such as the property changed deficiency, film stripping, and chemical proofing are reduced.When on the other hand, more than 15 mass parts, obtain not To the effect for reducing excessive gas, and then the light absorbs in film coated surface are aggravated, and there is the tendency that deep curability is reduced.More preferably For 0.5 ~ 10 mass parts.

As other can suitably the present invention resin combination used in Photoepolymerizationinitiater initiater, light-initiated auxiliary agent And sensitizer, benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal chemical combination can be included Thing, benzophenone cpd, tertiary amine compound and xanthone compound etc..

As benzoin compound, specifically, for example, benzoin, benzoin methylether, benzoin ethyl ether, benzene can be included Anisoin isopropyl ether etc..

As acetophenone compound, specifically, for example, acetophenone, 2,2- dimethoxy -2- phenyl benzene second can be included Ketone, 2,2- diethoxy -2- phenyl acetophenones, 1,1- dichloroacetophenones etc..

As anthraquinone compounds, specifically, for example, 2-methylanthraquinone, 2- EAQs, 2- tert-butyl anthracenes can be included Quinone, 1- chloroanthraquinones etc..

As thioxanthone compounds, specifically, for example, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthenes can be included Ketone, CTX, 2,4- diisopropylthioxanthones etc..

As ketal compound, specifically, for example, acetophenone dimethyl ketal, benzil dimethyl ketal can be included Deng.

As benzophenone cpd, specifically, for example can include benzophenone, 4- benzoyl diphenyl thioethers, 4- benzoyl -4 '-methyldiphenyl thioethers, 4- benzoyl -4 '-ethyl diphenyl sulfides, 4- benzoyl -4 '-propyl group hexichol Thioether etc..

As tertiary amine compound, specifically, for example, there are ethanolamine compound, the chemical combination with dialkylamino benzene structure Thing, for example, commercially available product can include 4,4 '-dimethylamino benzopheone（The NIS SOCURE of Japanese Cao Da companies manufacture MABP）, 4,4 '-lignocaine benzophenone（The EAB of Hodogaya Chemical Co., LTD. manufacture）Deng dialkylamino two Benzophenone, 7- (lignocaine) -4- methyl -2H-1- chromen-2-ones（7- (lignocaine) -4- methylcoumarins）Etc. containing There are the coumarin compound of dialkylamino, ethyl 4-dimethy laminobenzoate（The KAYACURE that Japanese chemical drug company system is made（Note Volume trade mark）EPA）, 2- dimethylamino ethyl benzoates（The manufacture of International Bio-Synthetics companies Quantacure DMB）, 4- dimethylamino benzoic acid (n-butoxy) ethyl esters（International Bio-Synthetics The Quantacure BEA of company's manufacture）, to dimethylamino benzoic acid isopentyl ethyl ester（What Japanese chemical drug company system was made KAYACURE DMBI）, 4- dimethylamino benzoic acid 2- Octyl Nitrites（The Esolol 507 of Van Dyk companies manufacture）、4, 4 '-lignocaine benzophenone（The EAB of Hodogaya Chemical Co., LTD. manufacture）Deng.

In the middle of these, preferred thioxanthone compounds and tertiary amine compound.Especially, it is excellent from from the aspect of the curability of deep Choosing includes thioxanthone compounds.Wherein, preferably comprise 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, CTX, The thioxanthone compounds such as 2,4- diisopropylthioxanthones.

It is aforementioned containing carboxy resin relative to 100 mass parts as the compounding amount of such thioxanthone compounds, preferably 20 Below mass parts.When the compounding amount of thioxanthone compounds is more than 20 mass parts, thick film curability is reduced, and can cause product Cost increases.Below more preferably 10 mass parts.

In addition, as tertiary amine compound, it is however preferred to have the compound of dialkylamino benzene structure, wherein, particularly preferred two The coumarin compound containing dialkylamino and perfume (or spice) of alkylamino benzophenone cpd, maximum absorption wavelength in 350 ~ 450nm Legumin ketone.

Used as dialkylamino benzophenone cpd, 4, the toxicity of 4 '-lignocaine benzophenone is also low, is preferred. Coumarin compound containing dialkylamino in ultraviolet range, therefore can be carried due to a length of 350 ~ 410nm of maximum absorption wave For colouring less, water white photosensitive composite is mathematical, it is also possible to provides using coloring pigment and reflects The coloring film of the color pigment color of itself.Particularly preferred 7- (lignocaine) -4- methyl -2H-1- chromen-2-ones.

It is aforementioned containing carboxy resin relative to 100 mass parts as the compounding amount of such tertiary amine compound, preferably 0.1 ~ 20 mass parts.When the compounding amount of tertiary amine compound is less than 0.1 mass parts, existing cannot be sufficiently sensitized the tendency of effect. During more than 20 mass parts, there is the tendency that deep curability is reduced.More preferably 0.1 ~ 10 mass parts.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can be used alone or with mixture of more than two kinds Form is used.

It is aforementioned containing carboxy resin relative to 100 mass parts, such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer Total amount is preferably below 35 mass parts.During more than 35 mass parts, exist causes what deep curability was reduced by their light absorbs Tendency.

Additionally, these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer are due to absorbing specific wavelength, therefore spirit sometimes Sensitivity step-down, can work as ultra-violet absorber.However, they are used not only for improving the sensitivity of composition.Can be with Absorb the light of specific wavelength as desired to improve the photoreactivity on surface, make film wire shaped and opening be changing into it is vertical Directly, taper, back taper, and improve live width, the machining accuracy in opening footpath.

In the middle of aforesaid Photoepolymerizationinitiater initiater, particularly preferably draw selected from the oxime ester system photopolymerization with oxime ester base Send out more than a kind in agent, alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, the group of acylphosphine oxide system Photoepolymerizationinitiater initiater composition Photoepolymerizationinitiater initiater.In the middle of these, the efficiency of initiator of oxime ester series initiators is good, can effectively improve sensitivity on a small quantity, It is few by pollution, volatilization caused by excessive gas during heat treatment after therefore epithelium against corrosion is formed, for the warpage for reducing epithelium is that have Effect, therefore it is preferred that.Further, thioxanthones system, coumarin series sensitizer for adjustment resist layer section shape it is effective, be excellent Choosing.Particularly preferably a combination of both is used.

Epoxy resin containing naphthalene nucleus used in the light solidifying/heat solidifying resin composition of the present invention is as it was previously stated, anti- Answering property well can be obtained quickly on the basis of reaction completes, and can obtain being amenable to the high heat-resisting film of thermal history, and then not only The coefficient of linear thermal expansion of gained cured coating film（Hereinafter referred to as CTE）It is low, and for the stress ten when lax solder resist solidifies Divide effective.As such epoxy resin containing naphthalene nucleus, for example, can include HP-4032（DIC（Strain）Manufacture）、HP-4700（DIC （Strain）Manufacture）、E SN-355（Dongdu is melted into（Strain）Manufacture）、ESN-375（Dongdu is melted into（Strain）Manufacture）、NC-7300（Japanization Medicine（Strain）Manufacture）Deng.As the material that can particularly preferably use, can include with naphthalene skeleton and aralkyl structure etc. Multifunctional type epoxides, its derivative.

Aforementioned containing carboxy resin relative to 100 mass parts, the compounding amount containing naphthalene nucleus epoxy resin is 5 mass parts ~ 60 mass Part the following is suitable, more than more preferably 10 mass parts and below 50 mass parts.During less than 5 mass parts, confirm less than , on the other hand, during more than 60 mass parts, there is its tack, the poor visualization for causing film in the effect containing naphthalene nucleus epoxy resin Deng anxiety, it is not preferable.

Further, in the light solidifying/heat solidifying resin composition of the present invention, can add to give heat resistance Thermocurable composition.As the heat curable component used in the present invention, it is possible to use blocked isocyanate compounds, amino tree Fat, maleimide compound, benzoxazine colophony, carbodiimide resin, cyclic carbonate compound, multi-functional epoxy's chemical combination Usual heat-curing resin known in thing, multifunctional oxetane compound, episulfide resin, melamine derivative etc.. Preferred heat curable component is that have more than 2 cyclic ether groups and/or cyclic thioether base in 1 molecule in the middle of these（Hereinafter referred to as For ring-type（Sulphur）Ether）Thermocurable composition.These have ring-type（Sulphur）The Thermocurable composition of ether is commercially sold Species it is more, its structure can be passed through and give various characteristic.

There are 2 with upper annular in such molecule（Sulphur）The Thermocurable composition of ether is that have more than 2 in molecule , the compound of any one or 2 kinds of groups in three-membered ring, four-membered ring or pentacyclic cyclic ether group or cyclic thioether base, example Compound, the i.e. multi-functional epoxy compound at least in molecule with more than 2 epoxy radicals can be such as included, is at least had in molecule There are the compound of more than 2 oxetanyls, i.e. multifunctional oxetane compound, there are more than 2 thioethers in molecule The compound of base, i.e. episulfide resin etc..

As aforementioned multi-functional epoxy compound, for example, can include the manufacture of Japan Epoxy Resins Co., Ltd.s JER（Registration mark）828th, jER834, jER 1001, jE R1004, the EPICLON of DIC companies manufacture（Registration mark） 840th, EPICLON 850, EPICLON 1050, EPICLON 2055, the Epo Tohto of Dongdu chemical conversion company manufacture（Registrar Mark）YD-011, YD-013, YD-127, YD-128, the D.E.R.317 of The Dow Chemical Company manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the Aral dite 6071 of Ciba Japan K.K. Corp., Aral dite 6084th, Araldite GY250, Araldite GY260, the Sumiepoxy ESA-011 of Sumitomo Chemical Co. Ltd.'s manufacture, ESA-014, ELA-115, ELA-128, industrial group of Asahi Chemical Industry manufacture A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 etc.（It is trade name）Bisphenol A type epoxy resin；Japan Epoxy Resins Co., Ltd. manufacture EPICLON 152, the EPICLON 165 of jERYL903, DIC company manufacture, the Epo Tohto of Dongdu chemical conversion company manufacture YDB-400, YDB-500, the D.E.R.542 of The Dow Chemical Company manufactures, Ciba Japan K.K. manufactures Araldite 8011, Sumiepoxy ESB-400, the E SB-700 of Sumitomo Chemical Co. Ltd.'s manufacture, industrial group of Asahi Chemical Industry A.E.R.711, A.E.R.714 of manufacture etc.（It is trade name）Brominated epoxy resin；Japan Epoxy Resins Co., Ltd. D.E.N.431, D.E.N.438 of jER152, the jER154 for manufacturing, The Dow Chemical Company manufactures, DIC EPICLON N-730, EPICLON N-770, the EPICLON N-865 of company's manufacture, the Epo of Dongdu chemical conversion company manufacture Tohto YDCN-701, YDCN-704, Araldite ECN1235, Araldite of Ciba Japan K.K. manufactures ECN1273, Araldite ECN1299, Araldite XPY307, the EPPN that Japanese chemical drug company system is made（Registration mark）- 201、EOCN（Registration mark）- 1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co. Ltd.'s manufacture Sumiepoxy ESCN-195X, ES CN-220, A.E.R.ECN-235, ECN-299 of the manufacture of industrial group of Asahi Chemical Industry etc.（ For trade name）Phenolic resin varnish type epoxy resin；EPICLON 830, the Japan Epoxy Resins Co. of DIC companies manufacture, Ltd. jER807, Epo Tohto YDF-170, YDF-175, the YDF-2004 of the manufacture of Dongdu chemical conversion company for manufacturing, Ciba Aral dite XPY306 of Japan K.K. manufactures etc.（It is trade name）Bisphenol f type epoxy resin；Dongdu is melted into company system Epo Tohto ST-2004, ST-2007, ST-3000 for making etc.（Trade name）Bisphenol-A epoxy resin；Japan The jER604 of Epoxy Resins Co., Ltd.s manufacture, the Epo Tohto YH-434, Ciba of the manufacture of Dongdu chemical conversion company Araldite MY720 of Japan K.K. manufactures, the Sumiepoxy ELM-120 of Sumitomo Chemical Co. Ltd.'s manufacture etc.（It is Trade name）Glycidyl amine type epoxy resin；The Araldite CY-350 of Ciba Japan K.K. manufactures（Trade name）Deng Hydantoins type epoxy resin；The CELLOXIDE of DAICEL CHEMICAL INDUSTRIES, LTD. manufacture（Registration mark） Aral dite CY 175, CY 179 of 2021, Ciba Japan K.K. manufactures etc.（It is trade name）Ester ring type asphalt mixtures modified by epoxy resin Fat；The YL-933 of Japan Epoxy Resins Co., Ltd.s manufacture, The Dow Chemical Company manufacture T.E.N., EPPN-501, EPPN-502 etc.（It is trade name）Trihydroxy benzene methylmethane type epoxy resin；Japan Epoxy YL-6056, YX-4000, YL-6121 of Resins Co., Ltd. manufacture（It is trade name）Deng di- cresols type or xenol Type epoxy resin or their mixture；The EBP S-200 that Japanese chemical drug company system is made, the EPX-30 of ADEKA companies manufacture, The EXA-1514 of DIC companies manufacture（Trade name）Deng bisphenol-s epoxy resin；Japan Epoxy Resins Co., Ltd. systems The jER 157S for making（Trade name）Etc. phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin；Japan Epoxy Resins Co., Ltd. are manufactured JERYL-931, the Araldite 163 etc. of Ciba Japan K.K. manufactures（It is trade name）Four hydroxy phenyl ethane type epoxies Resin；The Aral dite PT810 of Ciba Japan K.K. manufactures（Trade name）, the TEPIC of Nissan Chemical Industries company manufacture （Registration mark）Deng hetero ring type epoxy resin；The BLEMMER of Nof Corp.'s manufacture（Registration mark）The phthalic acids such as DGT 2-glycidyl ester resin；The four glycidyl group dimethylbenzene ethanes such as the ZX-1063 of Dongdu chemical conversion company manufacture (tetraglycidyl xylenoyl ethane) resin；ESN-190, ESN-360 of chemical company of Nippon Steel manufacture, DIC are public The epoxy resin containing naphthyl such as HP-4032, EXA-4750, EXA-4700 of department's manufacture；HP-7200, HP- of DIC companies manufacture The epoxy resin with bicyclopentadiene skeleton such as 7200H；The metering systems such as CP-50S, CP-50M of Nof Corp.'s manufacture Acid glycidyl ester copolymerization system epoxy resin；And, the copolymerization of N-cyclohexylmaleimide and GMA Epoxy resin；Epoxide modified polybutadiene rubber derivative（DAICEL CHEMICAL INDUSTRIES, LTD. manufacture PB-3600 etc.）, CTBN modified epoxies（Such as YR-102, YR-450 of the manufacture of Dongdu chemical conversion company etc.）Deng, but do not limit In these.These epoxy resin may be used singly or in combination of two or more.In the middle of these, particularly preferred phenolic aldehyde is clear Paint shaped epoxy resin, modified novolac type epoxy resin, hetero ring type epoxy resin, di- first phenol-type epoxy resin or they Mixture.

As aforementioned multifunctional oxetane compound, double [(3- methyl -3- oxetanyl methoxies can be included Base) methyl] ether, double [(3- ethyl -3- oxetanylmethoxies) methyl] ethers, the double [(3- methyl -3- oxa- ring fourths of 1,4- Alkyl methoxyl group) methyl] benzene, double [(3- ethyl -3- oxetanylmethoxies) methyl] benzene of 1,4-, acrylic acid (3- methyl - 3- oxetanyls) methyl esters, acrylic acid (3- ethyl -3- oxetanyls) methyl esters, methacrylic acid (3- methyl -3- oxygen Azetidinyl) methyl esters, methacrylic acid (3- ethyl -3- oxetanyls) methyl esters, their oligomer or copolymer etc. Multifunctional oxetanes class, can include in addition novolac resin, poly- (4-Vinyl phenol), cardo type bisphenols, cup Aromatic hydrocarbons, resorcinol calixarenes (calix resorcin arene) class or silsesquioxane (silsesquioxane) etc. Resin with hydroxyl and oxa- cyclobutanol（oxetanyl alcohol）Etherate etc..Additionally, can also include with oxygen The unsaturated monomer of azetidine ring with（Methyl）Copolymer of alkyl acrylate etc..

As in previous molecular have 2 with upper annular（Sulphur）The episulfide resin of ether, for example, can include Japan The YL7000 of Epoxy Resins Co., Ltd. manufacture（Bisphenol A-type episulfide resin）, Dongdu chemical conversion（Strain）Manufacture YSLV-120TE Deng.Alternatively, it is also possible to use the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced using same synthetic method Episulfide resin etc. into obtained from sulphur atom.

Relative to the aforementioned equivalent of carboxyl 1 containing carboxy resin, there are 2 with upper annular in previous molecular（Sulphur）The heat of ether The compounding amount of curability composition is preferably 0.6 ~ 2.5 equivalent, the scope of more preferably 0.8 ~ 2.0 equivalent.In molecule have 2 with Upper annular（Sulphur）When the compounding amount of the Thermocurable composition of ether is less than 0.6, carboxyl residual is had in soldering-resistance layer, it is heat resistance, resistance to Alkalescence, electrical insulating property etc. are reduced, and it is not preferable.When on the other hand, more than 2.5 equivalent, the ring-type of low-molecular-weight（Sulphur）Ether meeting In remaining in dry coating, so that apply film strength etc. reducing, it is not preferable.

Further, as the heat curable component that can suitably use, melamine derivative, benzoguanamine can be included and is spread out Biology etc..For example there are melamine methylol compound, methylolbenzoguanamine compound, methylol glycoluril compound and hydroxyl first Base urea compounds etc..Further, alkoxymethylated melamine compound, aikoxymethytated benzoguanamine compound, alkane Methylate glycoluril compounds and aikoxymethytated urea compounds of epoxide pass through respectively by melamine methylol compound, hydroxyl The methylol of methyl benzoguanamine compound, methylol glycoluril compound and hydroxymethyl urea compound is converted into alkoxy methyl And obtain.For the species of alkoxy methyl is not particularly limited, for example can using methoxy, ethoxyl methyl, third Epoxide methyl, butoxymethyl etc..Melamine particularly preferably to human body, eco-friendly formalin concentration below 0.2% Amine derivative.

As their commercially available product, for example, can include CYMEL（Registration mark）300、CYMEL 301、CYMEL 303、 CYMEL 370、CYMEL 325、CYMEL 327、CYMEL 701、CYMEL 266、CYMEL 267、CYMEL 238、CYMEL 1141、CYMEL 272、CYMEL 202、CYMEL 1156、CYMEL 1158、CYMEL 1123、CYMEL 1170、CYMEL 1174、CYMEL UFR65、CYMEL 300（Above Mitsui Cyanamid Ltd. are manufactured）, NIKALAC（Registration mark）Mx- 750、NIKALAC Mx-032、NIKALAC Mx-270、NIKALAC Mx-280、NIKALAC Mx-290、NIKALAC Mx- 706、NIKALAC Mx-708、NIKALAC Mx-40、NIKALAC Mx-31、NIKALAC Ms-11、NIKALAC Mw-30、 NIKALAC Mw-30HM、NIKALAC Mw-390、NIKALAC Mw-100LM、NIKALAC Mw-750LM（More than SANWACHEMICAL CO., LTD. are manufactured）Deng.

Above-mentioned heat curable component can be used alone or be applied in combination two or more.

In addition, in the light solidifying/heat solidifying resin composition of the present invention, can be in order to improve the solidification of composition Property and gained cured film obdurability and add and have in 1 molecule more than 2 NCOs or end-blockingization NCO Compound.For the compound in such 1 molecule with more than 2 NCOs or end-blockingization NCO, can Compound, the i.e. polyisocyanate compound in 1 molecule with more than 2 NCOs is included, or with 2 in 1 molecule Compound, i.e. blocked isocyanate compounds of end-blockingization NCO etc. more than individual.

As aforementioned polyisocyanates compound, for example, can use aromatic polyisocyanate, aliphatic polyisocyante Or ester ring type polyisocyanates.As the specific example of aromatic polyisocyanate, 4 can be included, 4 '-diphenyl methane two is different Cyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, naphthalene -1,5- diisocyanate, O-phthalic base two are different Cyanate, an xylylene diisocyanate and 2,4- toluene dimers.As the specific example of aliphatic polyisocyante, can Include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, tri-methyl hexamethylene two Isocyanates, 4,4- di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate) and IPDI.As ester ring type polyisocyanic acid The specific example of ester, can include bicycloheptane triisocyanate.And the isocyanate compound above enumerated can be included Adduct, biuret body and isocyanuric acid ester body.

The end-blockingization NCO contained in blocked isocyanate compounds is by NCO and end-capping reagent The group for reacting and being protected, be temporarily passivated.When set point of temperature is heated to, its end-capping reagent dissociates and generates isocyanates Base.

As blocked isocyanate compounds, addition reaction of the isocyanate compound with isocyanate-terminated dose can be used Product.As the isocyanate compound that can be reacted with end-capping reagent, isocyanurate type, biuret type can be included, add mould assembly Deng.As the isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyante or ester ring type can be used Polyisocyanates.As aromatic polyisocyanate, aliphatic polyisocyante, ester ring type polyisocyanates specific example, The compound as illustrated in above can be included.

As isocyanate-terminated dose, for example, can include the phenol such as phenol, cresols, xylenol, chlorophenol and ethyl -phenol It is end-capping reagent；The lactams system such as epsilon-caprolactams, δ-valerolactam, butyrolactam and azetidinone end-capping reagent；Acetyl second Acetoacetic ester and acetylacetone,2,4-pentanedione isoreactivity methylene base system end-capping reagent；Methyl alcohol, ethanol, propyl alcohol, butanol, amylalcohol, glycol monoethyl ether, second 2-ethoxyethanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl oxide, methyl glycollate, glycolic fourth The alcohol such as ester, diacetone alcohol, methyl lactate and ethyl lactate system end-capping reagent；Formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diethyl The oxime system such as acyl monoxime, hexamethylene oxime end-capping reagent；Butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, benzenethiol, methylbenzene phenyl-sulfhydrate, ethylo benzene The mercaptan such as thiophenol system end-capping reagent；The acid acid amides such as amide, benzamide system end-capping reagent；The acyl such as succinimide and maleimide Imines system end-capping reagent；The amine system end-capping reagent such as dimethylaniline, aniline, butylamine, dibutylamine；The imidazoles systems such as imidazoles, 2- ethyl imidazol(e)s End-capping reagent；The imines such as methylene imine and propylidene imines system end-capping reagent etc..

Blocked isocyanate compounds can be commercially available product, for example, can include Sumidur（Registration mark）BL- 3175、BL-4165、BL-1100、BL-1265、Desmodur（Registration mark）TPLS-2957、TPLS-2062、TPLS-2078、 TPLS-2117、DESMOTHERM2170、DESMOTHERM 2265（Above Sumitomo B ayer Urethane Co., Ltd. manufacture, trade name）, CORONATE（Registration mark）2512、CORONATE 2513、CORONATE 2520（Above Japan The manufacture of polyurethane industrial Co., Ltd., trade name）, B-830, B-815, B-846, B-870, B-874, B-882（Three wells force field Learn Co., Ltd.'s manufacture, trade name）, TPA-B 80E, 17B-60PX, E402-B 80T（Asahi Chemical Corp's manufacture, Trade name）Deng.Additionally, Sumidur BL-3175, BL-4265 are to use the first and second oximes as obtained from end-capping reagent.

There is more than 2 NCOs or the compound of end-blockingization NCO can individually make in above-mentioned 1 molecule It is applied in combination with a kind or by two or more.

It is aforementioned containing carboxy resin relative to 100 mass parts, there is more than 2 NCOs or envelope in such 1 molecule The compounding amount of the compound of endization NCO is 1 ~ 100 mass parts, the ratio of more preferably 2 ~ 70 mass parts is suitable. It is undesirable when aforementioned compounding amount is less than 1 mass parts, it is impossible to obtain the obdurability of sufficient film.On the other hand, exceed During 100 mass parts, storage stability is reduced, and it is not preferable.

In the light solidifying/heat solidifying resin composition of the present invention, can be in order to promote hydroxyl, carboxyl and isocyanic acid The curing reaction of ester group and add urethanation catalyst.As urethanation catalyst, preferably use and be selected from In the group of tin series catalysts, metal chloride, acetyl acetone salt, metal sulfate, amines or/and amine salt composition More than a kind urethanation catalyst.

As aforementioned tin series catalysts, for example, can include the organotin chemical combination such as stannous octoate, dibutyl tin laurate Thing, inorganic tin compound etc..

It is the chloride of the metal being made up of Cr, Mn, Co, Ni, Fe, Cu or Al as aforementioned metal chloride, for example may be used Include cobaltic chloride, nickel chloride, iron chloride etc..

It is the acetylacetone,2,4-pentanedione of the metal being made up of Cr, Mn, Co, Ni, Fe, Cu or Al as aforementioned acetyl acetone salt Salt, for example, can include acetylacetone cobalt, nickel acetylacetonate, ferric acetyl acetonade etc..

It is the sulfate of the metal being made up of Cr, Mn, Co, Ni, Fe, Cu or Al as aforementioned metal sulfate, for example may be used Include copper sulphate etc..

As amine compound, for example, can enumerate and have known triethylenediamine, N, N, N ', N '-tetramethyl- 1,6- hexamethylene diamines, double (2- dimethylaminoethyls) ethers, N, N, N ', N ", N "-five methyl diethylentriamine, N-methylmorpholine, N- Ethyl morpholine, N, N- dimethylethanolamines, dimorpholine base Anaesthetie Ether, N- methylimidazoles, dimethylamino naphthyridine, triazine, N '- (2- ethoxys)-N, N, N '-trimethyl-bis- (2- amino-ethyls) ethers, N, N- Exxal8 amine, N, N- Dimethylaminoethoxies Ethanol, N, N, N '-trimethyl-N '-(2- ethoxys) ethylene diamine, N- (2- ethoxys)-N, N ', N ", N "-tetramethyl two is sub- Ethyl triamine, N- (2- hydroxypropyls)-N, N ', N ", N "-tetramethyl diethylenetriamines, N, N, N '-trimethyl-N '-(2- hydroxyl second Base) propane diamine, N- methyl-N '-(2- ethoxys) piperazine, double (N, N- dimethylamino-propyl) amine, double (N, N- dimethylaminos third Base) isopropanolamine, the peaceful ring of 2- amino quinolines, the peaceful ring of 3- amino quinolines, the peaceful ring of 4- amino quinolines, the peaceful alcohol of 2- quinolines, the peaceful alcohol of 3- quinolines, 4- quinolines be peaceful Alcohol, 1- (2 '-hydroxypropyl) imidazoles, 1- (2 '-hydroxypropyl) -2-methylimidazole, 1- (2 '-ethoxy) imidazoles, 1- (2 '-hydroxyl second Base) -2-methylimidazole, 1- (2 '-hydroxypropyl) -2-methylimidazole, 1- (3 '-aminopropyl) imidazoles, 1- (3 '-aminopropyl) - 2-methylimidazole, 1- (3 '-hydroxypropyl) imidazoles, 1- (3 '-hydroxypropyl) -2-methylimidazole, N, N- dimethylamino-propyl-N '-(2- Ethoxy) amine, N, N- dimethylamino-propyl-N ', N '-bis- (2- ethoxys) amine, N, N- dimethylamino-propyl-N ', N '-bis- (2- Hydroxypropyl) amine, N, N- dimethylaminoethyl-N ', N '-bis- (2- ethoxys) amine, N, N- dimethylaminoethyl-N ', N '-bis- (2- Hydroxypropyl) amine, melamine or/and benzoguanamine etc..

As aforementioned amine salt, for example, can include DBU（Carbon -7- the alkene of 1,8- diazabicylos [5.4.0] 11）It is organic Amine salt of phosphate-gallate series etc..

The compounding amount of aforementioned urethanation catalyst is that the ratio of general amount is i.e. enough, such as relative to 100 matter Amount part contains carboxy resin（A）, preferably 0.1 ~ 20 mass parts, more preferably 0.5 ~ 10.0 mass parts.

Using in above-mentioned molecule have 2 with upper annular（Sulphur）During the Thermocurable composition of ether, heat cure is preferably comprised Catalyst.As such thermal curing catalyst, for example can include imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2- ethyls- 4-methylimidazole, 2- phenylimidazoles, 4- phenylimidazoles, 1- cyano ethyl -2- phenylimidazoles, 1- (2- cyano ethyls) -2- ethyls - The imdazole derivatives such as 4-methylimidazole；Dicyandiamide, benzyl dimethylamine, 4- (dimethylamino)-N, N- dimethyl benzyl amines, 4- methoxies The amines such as base-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amines, adipic dihydrazide, the acyl of decanedioic acid two The hydrazide compounds such as hydrazine；Phosphorus compounds such as triphenylphosphine etc..In addition, as commercially available product, such as four countries' chemical conversion can be included 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ of industrial group's manufacture（It is the trade name of imidazole compound）, San- The U-CAT of Apro Ltd. manufactures（Registration mark）3503N、U-CAT3502T（It is the blocked isocyanate compounds of dimethylamine Trade name）、DBU、DBN、U-CATSA102、U-CAT5002（It is two ring type amidine compounds and its salt）Deng.Especially do not limit In these, it is epoxy resin, the thermal curing catalyst of oxetane compound or is to promote epoxy radicals and/or oxa- ring The material of butane group and carboxyl reaction, exclusive use or two or more is used in mixed way also it doesn't matter.Alternatively, it is also possible to Using guanamines, methyl guanamines, benzoguanamine, melamine, 2,4- diaminourea -6- methacryloxyethyls-s-triazine, 2- Vinyl -2,4- diaminourea-s-triazine, 2- vinyl -4,6- diaminourea-s-triazine isocyanuric acid adduct, 2,4- diaminos The Striazine derivatives such as base -6- methacryloxyethyls-s-triazine isocyanuric acid adduct, preferably using these also as The compound that adaptation imparting agent works is applied in combination with aforementioned thermal curing catalyst.

The compounding amount of these thermal curing catalysts is that the ratio of common amount is i.e. enough, for example, is contained relative to 100 mass parts There are 2 with upper annular in carboxy resin or molecule（Sulphur）The Thermocurable composition of ether, preferably 0.1 ~ 20 mass parts, it is more excellent Elect 0.5 ~ 15.0 mass parts as.

The Photocurable resin composition of the present invention can be compounded colouring agent.As colouring agent, it is possible to use red, blue, green, Usual colouring agent, can be any one in pigment, dyestuff, pigment known in Huang etc..Specifically, can include and be endowed Such Colour Index below（C.I.；The S ociety of Dyers and Colourists are issued）Number material.Its In, from the viewpoint of the reduction from carrying capacity of environment and the impact to human body, preferably do not contain halogen.

Red stain：

As red stain, there are monoazo system, bisazo system, azo lake system, benzimidazolone Xi, perylenes system, diketone Base pyrrolopyrrole system, condensation azo system, anthraquinone system, quinacridone etc., specifically, can include be endowed it is following so Colour Index（C.I.；The Society of Dyers and Colourists are issued）Number material.

Monoazo system：Paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114, 146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269。

Bisazo system：Pigment red 37,38,41.

Monoazo color lake is：Pigment red 48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、52:2、53:1、 53:2、57:1、58:4、63:1、63:2、64:1、68。

Benzimidazolone system：Paratonere 171, paratonere 175, paratonere 176, paratonere 185, paratonere 208.

Perylene system：Solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, pigment Red 179, paratonere 190, paratonere 194, paratonere 224.

Diketopyrrolopyrrolecocrystals system：Paratonere 254, paratonere 255, paratonere 264, paratonere 270, paratonere 272.

Condensation azo system：Paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221st, paratonere 242.

Anthraquinone system：It is paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, solvent red 52, molten Agent red 207.

Quinacridone：Pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209.

Blue colorant：

As blue colorant, there are phthalocyanine system, anthraquinone system etc., pigment system can be included and be classified as pigment（Pigment） Compound, specifically, following this materials can be included：Pigment blue 15, pigment blue 15:1st, pigment blue 15:2nd, alizarol saphirol 15:3rd, pigment blue 15:4th, pigment blue 15:6th, pigment blue 16, pigment blue 60.

As dyestuff system, it is possible to use solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent Blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc..In addition to the foregoing, Can also be replaced using metal or unsubstituted phthalocyanine compound.

Green colourant：

As green colourant, equally there are phthalocyanine system, anthraquinone Xi, perylenes system, specifically, it is possible to use pigment Green 7, pigment Green 36, solvent green 3, solvent be green 5, solvent is green 20, solvent green 28 etc..In addition to the foregoing, can also using metal replace or Unsubstituted phthalocyanine compound.

Yellow colorants：

As yellow colorants, there are monoazo system, bisazo system, condensation azo system, benzimidazolone system, isoindolinone System, anthraquinone system etc., specifically, can include following material.

Anthraquinone system：Solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, face Material yellow 202.

Isoindolinone system：Pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185.

Condensation azo system：Pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, pigment yellow 166, Pigment yellow 180.

Benzimidazolone system：Pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181。

Monoazo system：Pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1、65、73、74、75、97、100、104、 105、111、116、167、168、169、182、183。

Bisazo system：Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174, 176、188、198。

Furthermore, it is possible to add the colouring agent of purple, orange, palm fibre, black etc. in order to adjust tone.

If particular instantiation, there is a pigment violet 19,23,29,32,36,38,42, solvent violet 13,36, C.I. pigment oranges 1, C.I. pigment orange 5, C.I. pigment orange 13s, C.I. pigment oranges 14, C.I. pigment oranges 16, C.I. pigment oranges 17, C.I. pigment oranges 24, C.I. pigment orange 34, C.I. pigment orange 36s, C.I. pigment oranges 38, C.I. pigment oranges 40, C.I. pigment oranges 43, C.I. pigment oranges 46th, C.I. pigment oranges 49, C.I. pigment orange 5s 1, C.I. pigment oranges 61, C.I. pigment oranges 63, C.I. pigment oranges 64, C.I. pigment Orange 71, C.I. pigment oranges 73, C.I. pigment browns 23, C.I. pigment brown 25s, C.I. pigment blacks 1, C.I. pigment blacks 7 etc..

The compounding ratio of aforementioned such colouring agent is not particularly limited, aforementioned containing carboxy resin relative to 100 mass parts, The ratio of preferably 0 ~ 10 mass parts, particularly preferably 0.1 ~ 5 mass parts is i.e. enough.

There are more than 2 ethene insatiable hungers in molecule used in the light solidifying/heat solidifying resin composition of the present invention With the compound of group be by active energy beam irradiation carry out photocuring make it is aforementioned containing carboxy resin insoluble in aqueous alkali, Or contribute to aforementioned containing the thawless compound of carboxy resin.As such compound, it is possible to use known usual polyester （Methyl）Acrylate, polyethers（Methyl）Acrylate, carbamate（Methyl) acrylate, carbonic ester（Methyl）Acrylic acid Ester, epoxy（Methyl）Acrylate etc., specifically, can include the hydroxyls such as acrylic acid 2- hydroxyl ethyl esters, acrylic acid 2- hydroxypropyl acrylates Alkylacrylate；The diacrylate esters of the glycol such as ethylene glycol, methoxyl group TEG, polyethylene glycol, propane diols；N,N- The acrylic amides such as DMAA, N hydroxymethyl acrylamide, N, N- dimethylamino propyl acrylamides；Acrylic acid N, The acrylate classes such as N- dimethylaminoethyls, acrylic acid N, N- dimethylamino propyl ester；Hexylene glycol, trihydroxy methyl third The polyalcohols such as alkane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct, epoxy The multicomponent methacrylate class of propane addition product or 6-caprolactone addition product etc.；Phenoxy group acrylate, bisphenol a diacrylate, With the multicomponent methacrylate class of the ethylene oxide adduct or propylene oxide adduct of these phenols etc.；Glycerine 2-glycidyl The glycidol ethers such as ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester Multicomponent methacrylate class；Be not limited to it is above-mentioned, it is many to PPG, PCDL, C-terminal polybutadiene, polyester The polyalcohols such as first alcohol directly carry out acroleic acid esterification or carry out urethane acrylate using diisocyanate and obtain Esters of acrylic acid and melamine acrylate, and/or each methyl acrylic ester corresponding to aforesaid propylene esters of gallic acid etc..

Further, the polyfunctional epoxy resins such as acrylic acid and cresol novolak type epoxy resin of sening as an envoy to can be enumerated to react and obtain The Epocryl for arriving, further makes hydroxyl and pentaerythritol triacrylate of the Epocryl etc. Obtained from the half carbamate compounds reaction of the diisocyanate such as hydroxy acrylate and IPDI Epoxy amino formic acid esters acrylate compounds etc..Such epoxy acrylate system resin can improve photo-curable without Reduce dry to touch.

It is aforementioned containing carboxy resin relative to 100 mass parts, there are more than 2 ethene unsaturated groups in such molecule The compounding amount of compound be 5 ~ 100 mass parts, the ratio of more preferably 1 ~ 70 mass parts.Aforementioned compounding amount is less than 5 mass parts When, photo-curable is reduced, it becomes difficult to which the alkali development after active energy beam irradiates carries out pattern and formed, and it is not preferable. And during more than 100 mass parts, the dissolubility of aqueous alkali is reduced, film becomes fragile, and it is not preferable.

The light solidifying/heat solidifying resin composition of the present invention can be in order to improve the physical strength etc. of its film and root According to need be compounded filler.As such filler, it is possible to use known usual inorganic or organic filler, particularly preferably using sulphur Sour barium, preparing spherical SiO 2 and talcum.Further, in order to obtain white outward appearance, anti-flammability, titanium oxide, metal can be aoxidized The metal hydroxides such as thing, aluminium hydroxide are used as extender pigment filler.It is aforementioned containing carboxy resin relative to 100 mass parts, these The compounding amount of filler is preferably below 200 mass parts, more preferably 0.1 ~ 150 mass parts, particularly preferably 1 ~ 100 mass parts. When the compounding amount of filler is more than 200 mass parts, the viscosity of composition is uprised, printing is reduced, or solidfied material becomes fragile, therefore unexcellent Choosing.

Further, light solidifying/heat solidifying resin composition of the invention can be in order to improve dry to touch, at improvement Rationality etc. and use binder polymer.Polyester based polymer, polyurethane series polymer, Amino-Polyester formic acid can for example be used Ester based polymer, polyamide-based polymer, polyesteramide based polymer, acrylic acid series polymeric compounds, cellulose-based polymer, poly- breast Sour based polymer, phenoxy group based polymer etc..These binder polymers can be used alone or with mixture of more than two kinds Form is used.

Further, light solidifying/heat solidifying resin composition of the invention can be in order to give flexibility, improve solidfied material Fragility etc. and use hydroxyl elastomer, other elastomers.For example can be using polyester-based elastomer, polyurethane series elasticity Body, polyester urethane based elastomers, polyamide-based elastomer, polyesteramide based elastomers, acrylic elastomer, alkene Based elastomers.Alternatively, it is also possible to using with two terminal carboxylic's modified version nitrile rubbers by the epoxy resin with various skeletons Resin etc. obtained from part or all is epoxy-modified.Further, it is also possible to using the elasticity of the polybutadiene system containing epoxy radicals Body, the polybutadiene based elastomers containing acryloyl group etc..These elastomers can be used alone or with mixture of more than two kinds Form is used.

Further, light solidifying/heat solidifying resin composition of the invention can be above-mentioned containing carboxy resin, system in order to synthesize For composition or use organic solvent to be applied in substrate, carrier film to adjust viscosity.

As such organic solvent, ketone, aromatic hydrocarbon, gylcol ether, glycol ether acetate can be included Class, esters, alcohols, aliphatic hydrocarbon, oil series solvent etc..More specifically, there are the ketones such as MEK, cyclohexanone；Toluene, diformazan Benzene, durene etc. are aromatic hydrocarbon；Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl card must The glycol ethers such as alcohol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether；Acetic acid second Ester, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether second The esters such as acid esters；The alcohols such as ethanol, propyl alcohol, ethylene glycol, propane diols；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, hydrogen Oil series solvent such as naphtha, solvent naphtha etc..Such organic solvent can be used alone or with mixture of more than two kinds Form use.

Generally, many macromolecular materials succeedingly will occur oxidative degradation interlock type once oxidation, cause height The function of molecular material is reduced, therefore in the light solidifying/heat solidifying resin composition of the present invention, can be for anti-block Change and add（1）By the radical scavenger of produced free radical ineffective treatment or/and（2）Produced peroxide is decomposed Into antioxidants such as harmless material, the peroxide decomposers for not producing new free radical.

For the antioxidant worked as radical scavenger, as specific compound, quinhydrones, 4- can be included Tert-butyl catechol, TBHQ, hydroquinone monomethyl ether, DBPC 2,6 ditertiary butyl p cresol, 2,2- methylene-bis--(4- first Base -6- tert-butyl phenols), 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 1,3,5- trimethyl -2,4,6- Three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, 1,3,5- tri- (3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl)-guanamine, 4, The phenol systems such as 6- (1H, 3H, 5H) triketone, p methoxy phenol（メタキノン）, the quinone based compound such as benzoquinones, double (2,2,6,6- Tetramethyl -4- piperidyls) amine compound such as-sebacate, phenthazine etc..

Radical scavenger can be commercially available product, for example, can include ADK STAB（Registration mark）AO-30、ADK STAB AO-330、ADK STAB AO-20、ADK STAB LA-77、ADK STAB LA-57、ADK STAB LA-67、ADK STAB LA-68、ADK STAB LA-87（The manufacture of above ADEKA company, trade name）, IRGANOX（Registration mark）1010、 IRGANOX 1035、IRGANOX 1076、IRGANOX 1135、TINUVIN（Registration mark）111FDL、TINUVIN 123、 TINUVIN 144、TINUVIN 152、TINUVIN 292、TINUVIN 5100（Above Ciba Japan K.K. manufactures, commodity Name）Deng.

For the antioxidant worked as peroxide decomposer, as specific compound, triphen can be included The phosphorus series compounds such as base phosphite ester, pentaerythrite four (lauryl thiopropionate), dilauryl thiodipropionate, 3,3 '- Chalcogenide compounds such as the double octadecyl esters of thio-2 acid etc..

Peroxide decomposer can be commercially available product, for example, can include ADKS TAB TPP（ADEKA company systems Make, trade name）, MARK AO-412S（Adeka Argus Chemical Co., Ltd. manufacture, trade name）, SUMILIZER （Registration mark）TPS（Sumitomo chemical company manufacture, trade name）Deng.

Above-mentioned antioxidant may be used singly or in combination of two or more.

In addition, can absorb light generally, due to macromolecular material and thus decompose, deteriorate, therefore in the light of the present invention In curability hot curing resin composition, can in order to carry out for ultraviolet stabilisation countermeasure and in above-mentioned antioxidant Outside use ultra-violet absorber.

As ultra-violet absorber, benzophenone derivates, benzoate derivatives, BTA can be included and derived Thing, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, anthranilate derivatives, dibenzoyl first Alkane derivatives etc..As the specific example of benzophenone derivates, ESCALOL 567,2- can be included Hydroxyl -4- oxy-octyl benzophenones, 2,2 '-dihydroxy -4- methoxy benzophenones and 2,4 dihydroxyl benzophenone etc..Make For the specific example of benzoate derivatives, BMDBM, phenyl salicylate, salicylic acid can be included to tertiary fourth Base phenyl ester, 2,4- di-tert-butyl-phenyls -3,5- di-tert-butyl-4-hydroxybenzoic acids ester and cetyl -3,5- di-t-butyl -4- Hydroxybenzoate etc..As the specific example of benzotriazole derivatives, can include 2- (2 '-hydroxyl -5 '-tert-butyl benzene Base) BTA, 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyl-the 3 '-tert-butyl group -5 '-methylbenzenes Base) -5- chlorobenzotriazoles, 2- (2 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) -5- chlorobenzotriazoles, 2- (2 '-hydroxyl -5 '-first Base phenyl) BTA and 2- (2 '-hydroxyl -3 ', 5 '-di-tert-pentyl-phenyl) BTA etc..As the tool of pyrrolotriazine derivatives The example of body, can include hydroxyphenyltriazinuv, Tinosorb S etc..

Can be commercially available product as ultra-violet absorber, for example, can include TINUVIN PS, TINUVIN 99- 2、TINUVIN 109、TINUVIN 384-2、TINUVIN 900、TINUVIN 928、TINUVIN 1130、TINUVIN 400、 TINUVIN 405、TINUVIN 460、TINUVIN 479（Above Ciba Japan K.K. manufactures, trade name）Deng.

Above-mentioned ultra-violet absorber can be used alone or be applied in combination two or more, by with aforementioned antioxidant It is applied in combination, the stabilisation of molding obtained by the light solidifying/heat solidifying resin composition of the present invention can be sought.

In the light solidifying/heat solidifying resin composition of the present invention, in order to improve sensitivity, it is possible to use as chain Known usual N-phenylglycine class, phenoxy acetic acids, thio phenoxy acetic acids, thyroidan of transfer agent etc..Lift If going out the specific example of chain-transferring agent, for example have mercapto succinic acid, TGA, mercaptopropionic acid, methionine, cysteine, The chain-transferring agent with carboxyl such as thiosalicylic acid and its derivative；Mercaptoethanol, mercaprol, Mercaptobutanol, sulfydryl the third two The chain-transferring agents with hydroxyl such as alcohol, sulfydryl butanediol, hydroxy benzenes mercaptan and its derivative；1- butyl mercaptan, butyl -3- sulfydryls third Acid esters, methyl -3-thiopropionate, 2,2- (ethylidene dioxy) diethyl mercaptan, ethyl mercaptan, 4- methylbenzenethiols, dodecyl Mercaptan, propanethiol, butyl mercaptan, amyl hydrosulfide, 1- spicy thioalcohols, cyclopentanethiol, cyclohexylmercaptan, thio glycerine, 4,4- thiobis benzene Mercaptan etc..

Further, it is possible to use multi-functional mercaptan based compound, it is not particularly limited, for example can using 1,6- oneself The analiphatic sulphur alcohols such as two mercaptan, the mercaptan of 1, the 10- last of the ten Heavenly stems two, dimercapto diethyl ether, dimercapto diethyl base thioether, the sulphur of xyxylene two The aromatic mercaptans classes such as alcohol, 4,4 '-dimercapto diphenyl sulfide, 1,4- dimercaptobenzenes；Ethylene glycol double (TGA) ester, poly- second two Double (TGA) esters of alcohol, propane diols double (TGA) ester, glycerine three (TGA) ester, trimethylolethane trimethacrylate (mercaptos Guanidine-acetic acid) ester, trimethylolpropane tris (TGA) ester, pentaerythrite four (TGA) ester, (the sulfydryl of dipentaerythritol six Acetic acid) polyalcohol such as ester many (TGA) esters；Double (3- mercaptopropionic acids) esters of ethylene glycol, double (the 3- sulfydryls third of polyethylene glycol Acid) ester, propane diols double (3- mercaptopropionic acids) ester, glycerine three (3- mercaptopropionic acids) ester, trimethylolethane trimethacrylate (mercaptopropionic acid) Ester, trimethylolpropane tris (3- mercaptopropionic acids) ester, pentaerythrite four (3- mercaptopropionic acids) ester, (the 3- sulfydryls of dipentaerythritol six Propionic acid) polyalcohol such as ester many (3- mercaptopropionic acids) esters；1,4- double (3- sulfydryl butyryl acyloxies) butane, (the 3- mercaptos of 1,3,5- tri- Base butoxyethyl group) many (mercaptos such as -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, pentaerythrite four (3- mercaptobutyric acids) ester Base butyric acid) esters.

As their commercially available product, for example can include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEM PIC（Above Sakai chemical industry（Strain）Manufacture）, Karenz（Registration mark）MT-PE1, Karenz MT-BD1 and Karenz-NR1（Above Showa electrician（Strain）Manufacture）Deng.

Further, for the heterocyclic compound with sulfydryl worked as chain-transferring agent, for example, sulfydryl -4- can be included Butyrolactone（Another name：2- sulfydryls -4- butyrolactone (butanolide)）, 2- sulfydryl -4- methyl -4- butyrolactone, 2- sulfydryl -4- second Base -4- butyrolactone, 2- sulfydryl -4- thiobutryolacatones, 2- sulfydryl -4- butyrolactams, N- methoxyl group -2- sulfydryl -4- butyrolactams, N- ethyoxyl -2- sulfydryl -4- butyrolactams, N- methyl -2- sulfydryl -4- butyrolactams, N- ethyl -2- sulfydryl -4- butyrolactams, N- (2- methoxyl groups) ethyl -2- sulfydryl -4- butyrolactams, N- (2- ethyoxyls) ethyl -2- sulfydryl -4- butyrolactams, 2- sulfydryls - 5- valerolactones, 2- sulfydryl -5- valerolactams, N- methyl -2- sulfydryl -5- valerolactams, N- ethyl -2- sulfydryl -5- valerolactams, N- (2- methoxyl groups) ethyl -2- sulfydryl -5- valerolactams, N- (2- ethyoxyls) ethyl -2- sulfydryl -5- valerolactams, 2- sulfydryls Benzothiazole, 2- sulfydryl -5- methyl mercapto thiadiazoles, 2- sulfydryl -6- caprolactams, 2,4,6- tri-thiol s-triazine（The chemical conversion of three associations （Strain）Manufacture：Trade name Zisnet F）, 2- dibutylamino -4,6- dimercapto s-triazine（The chemical conversion of three associations（Strain）Manufacture：Trade name Zisnet DB）With 2- anilino- -4,6- dimercapto s-triazine（The chemical conversion of three associations（Strain）Manufacture：Trade name Zisnet AF）.

Especially, there is mercapto as the chain-transferring agent of the developability without compromising on light solidifying/heat solidifying resin composition The heterocyclic compound of base, preferred mercaptobenzothiazoler, 3- sulfydryl -4- methyl -4H-1,2,4- triazoles, 5- methyl isophthalic acids, 3,4- thiophenes two Azoles -2- mercaptan, 1- phenyl -5- sulfydryls -1H-TETRAZOLE.These chain-transferring agents can be used alone or be applied in combination two or more.

In the light solidifying/heat solidifying resin composition of the present invention, in order to improve the adaptation of interlayer or can feel The adaptation of photosensitive resin layer and base material and use closely sealed accelerator.Specifically enumerate if example, for example, have benzimidazole, benzo Oxazole, benzothiazole, 2-mercaptobenzimidazole, 2- mercaptobenzoxazoles, 2-mercaptobenzothiazole（Trade name：Kawaguchi's chemistry work Industry（Strain）The Accel M of manufacture）, 3- morpholinomethyls -1- phenyl-triazole -2- thioketones, 5- amino -3- morpholinomethyls-thiophene Azoles -2- thioketones, 2- sulfydryls -5- methyl mercaptos-thiadiazoles, triazole, tetrazolium, BTA, carboxyl benzotriazole, the benzo containing amino Triazole, silane coupler etc..

The light solidifying/heat solidifying resin composition of the present invention further can as desired add micro mist titanium dioxide The thixotropic agent such as silicon, organobentonite, montmorillonite, hydrotalcite.On the ageing stability as thixotropic agent preferred organobentonite, The electrical characteristics of hydrotalcite, particularly hydrotalcite are excellent.Furthermore it is possible to hot polymerization inhibitor is compounded, silicon systems, fluorine system, macromolecular etc. The silane coupler of defoamer and/or levelling agent, imidazoles system, thiazole system, triazole system etc., antirust agent, also bis-phenol system, triazine sulphur The known usual additive kind of the copper deactivator of alcohol system etc. or the like.

Aforementioned hot polymerization inhibitor can be used to be polymerized when the thermal polymerization or the Jing that prevent aforementioned polymeric compound.As Hot polymerization inhibitor, for example, can include 4- metoxyphenols, quinhydrones, alkyl or aryl and replace quinhydrones, tert-butyl catechol, adjacent benzene three Phenol, 2- dihydroxy benaophenonels, 4- methoxyl group -2- dihydroxy benaophenonels, cuprous salinization, phenthazine, tetrachloroquinone, naphthylamines, β-naphthalene Phenol, 2,6- di-t-butyl -4- cresols, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols), pyridine, nitrobenzene, dinitro The reactant of benzene, picric acid, 4- toluidines, methylenum careuleum, copper and organic sequestering agent, gaultherolin and phenthazine, nitroso Chelate of compound, nitroso compound and Al etc..

The light solidifying/heat solidifying resin composition of the present invention for example can be adjusted to suitable painting with aforementioned organic solvents The viscosity of cloth method, by methods such as dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain coatings base is applied to On material, the organic solvent volatile dry included in composition is made at a temperature of about 60 ~ 100 DEG C（Preliminarily dried）, thus shape Into not viscous film.Hereafter, by contact（Or cordless）Through define the photomask of pattern optionally by Active energy beam is exposed or directly carries out pattern exposure using the direct exposure machine of laser, by aqueous alkali（For example 0.3 ~ 3wt% aqueous sodium carbonates）Unexposed portion is developed and corrosion-resisting pattern is formed.Further, it is the group containing Thermocurable composition During compound, for example, its heat cure is made by being heated to about 130 ~ 180 DEG C of temperature, make the carboxyl containing carboxy resin and molecule In there is the Thermocurable composition reaction of more than 2 cyclic ether groups and/or cyclic thioether base, heat resistance, chemically-resistant can be formed The cured coating film of all excellents such as medicine, resistance to hygroscopicity, adaptation, electrical characteristics.Even if additionally, without Thermocurable into Timesharing, by being heat-treated, the ethene unsaturated bond of the photo-curable composition remained with unreacted state when making exposure Hot radical polymerization is carried out, coating characteristic also can be improved, therefore can be heat-treated according to purpose and purposes（Heat cure）.

As above-mentioned base material, it is possible to use be pre-formed with printed circuit board (PCB), the flexible print wiring board of circuit, additionally Can use the copper-clad laminated board of all grades (FR-4 etc.), Kapton, PET film, glass substrate, ceramic substrate, Wafer board etc., the copper-clad laminated board is using paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-poly- Acid imide, glass cloth/non-woven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthetic fibers-epoxy resin, fluororesin gather Obtained from the composites such as ethene PPO cyanates.

The volatile dry carried out after the light solidifying/heat solidifying resin composition of the coating present invention can use hot blast Circulating drying oven, IR stoves, heating plate, convective oven etc.（Using the thermal source with the air mode of heating using steam Device makes the method that the hot air convection in drying machine contacts and by way of nozzle blows supporter）Come carry out.

After the light solidifying/heat solidifying resin composition and volatile dry of the following coating present invention, gained film is entered Row exposure（The irradiation of active energy beam）.The exposure portion of film（The part being irradiated to by active energy beam）Solidification.

As the exposure machine used in the irradiation of above-mentioned active energy beam, it is possible to use direct drawing apparatus（For example pass through CAD data from computer carrys out the laser direct imaging device of depiction picture with Direct Laser）, be equipped with metal halide lamp Exposure machine, it is equipped with（It is super）The exposure machine of high-pressure sodium lamp, the exposure machine for being equipped with mercury short arc lamp lamp, use（It is super）High-pressure mercury The direct drawing apparatus of the ultraviolet lamps such as lamp.As active energy beam, as long as using maximum wavelength in the range of 350 ~ 410nm Laser, then can be any one in gas laser, Solid State Laser.In addition, its light exposure is different according to thickness etc., lead to Often can be set as 5 ~ 500mJ/cm², be preferably 10 ~ 300mJ/cm²In the range of.As above-mentioned direct drawing apparatus, for example may be used To use the device of Japan's Orbotech Ltd. manufactures, PENTAX CORPORATION manufactures etc., as long as generation can be vibrated most Big wavelength is the device of the laser beam of 350 ~ 410nm, then can use any device.

As aforementioned developing method, can be based on infusion process, elution method, spray-on process, spread coating etc., as developer solution, can With using the aqueous alkali of potassium hydroxide, NaOH, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, amine etc..

The present invention light solidifying/heat solidifying resin composition except the method on base material is coated directly onto with liquid with Outward, can be used with the form with dry film, the dry film has the painting on the film of polyethylene terephthalate etc. in advance Cloth solder resist and the solder mask for being dried and being formed.It is described below using the present invention light solidifying/heat solidifying resin composition as The situation that dry film is used.

There is dry film the strippable cover layer for stacking gradually carrier film and solder mask and using as desired to form Structure.Solder mask is the light solidifying/heat solidifying resin composition of alkali-developable to be coated in carrier film or cover layer simultaneously Layer obtained from drying.Formed on a carrier film after solder mask, laminated cover film thereon, or welding resistance is formed on cover layer It is layer, the laminate layers are folded on a carrier film, you can to obtain dry film.

As carrier film, the thermoplastic films such as the polyester film of 2 ~ 150 μ m-thicks can be used.

Solder mask is formed as follows：With knife type coater, lip coating machine（lip coater）, comma coater（comma coater）, film coater etc. by alkali-developable light solidifying/heat solidifying resin composition in carrier film or cover layer with 10 ~ 150 μm of thickness even spread, drying and formed.

As cover layer, it is possible to use polyethylene film, polypropylene film etc., it compares carrier film with the bonding force of solder mask Little with the bonding force of solder mask is preferable.

In order that making diaphragm on a printed circuit with dry film（Permanent diaphragm）, cover layer is peeled off, by solder mask It is Chong Die with the substrate for being formed with circuit, fitted using laminating machine etc., solder mask is thus formed on the base material for be formed with circuit. For the solder mask for being formed, it is exposed in the same manner as aforementioned, develops, is heating and curing, you can forms cured coating film.Carrier film Arbitrary period before exposure or after exposure peels off.

Embodiment

Embodiment described below and comparative example to the present invention being specifically described, but without doubt, the present invention is simultaneously It is not limited to following embodiments.Additionally, " part " and " % " for recording below, all quality in the case of without special declaration Benchmark.

Synthesis example 1

Add in the autoclave equipped with thermometer, nitrogen gatherer and epoxyalkane gatherer and agitating device 119.4 part phenolic varnish type cresol resin（Showa macromolecule（Strain）Manufacture, trade name：" Shonol CRG951 ", OH equivalents： 119.4）, 1.19 parts of potassium hydroxide and 119.4 parts of toluene, while stirring to carrying out nitrogen displacement, heat temperature raising in system.Connect , be slowly added dropwise 63.8 parts of expoxy propane, in 125 ~ 132 DEG C, 0 ~ 4.8kg/cm²Lower reaction 16 hours.Hereafter, it is cooled to room Temperature, 1.56 part of 89% phosphoric acid of addition mixing neutralizes in potassium hydroxide in the reaction solution, obtains nonvolatile component 62.1%, hydroxyl value For the propylene oxide reaction solution of the phenolic varnish type cresol resin of 182.2g/eq..The average addition of its every 1 equivalent phenolic hydroxyl group 1.08 mol of alkylene oxide hydrocarbon.

Then, by the epoxyalkane reaction solution of 293.0 parts of gained phenolic varnish type cresol resins, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acids, 0.18 part of methylnaphthohydroquinone and 252.9 parts of toluene are added to and are blown into pipe equipped with mixer, thermometer and air Reactor in, air is blown into the speed of 10ml/ minutes, while stirring 110 DEG C react 12 hours.For by reaction The water of generation, as the azeotropic mixture with toluene 12.6 parts of water are distilled out.Hereafter, room temperature is cooled to, by gained reaction solution Neutralized with 35.35 part of 15% sodium hydrate aqueous solution, then washed.Hereafter, with evaporimeter by toluene side with 118.1 part two Ethylene glycol monoethyl ether acetate displacement side is distilled off, and obtains phenolic varnish type acrylic ester resin solution.Then, by 332.5 Phenolic varnish type acrylic ester resin solution and 1.22 parts of triphenylphosphines are added to equipped with agitator, thermometer and air obtained by part In being blown into the reactor of pipe, air is blown into the speed of 10ml/ minutes, 60.8 parts of tetrahydrochysene O-phthalics are slowly added to while stirring Acid anhydrides, reacts 6 hours at 95 ~ 101 DEG C.Obtain the acid number 88mgKOH/g of solid constituent, nonvolatile component 71% containing carboxyl The resin solution of photoresist.Hereinafter referred to as varnish A-1.

Synthesis example 2

Put into as polymer polyol in 5 liters equipped with thermometer, mixer and reflux cooler of removable flasks 1245 parts of polycaprolactone glycols of alcohol（PLACCEL208, the molecular weight of DAICEL CHEMICAL INDUSTRIES, LTD. manufacture 830）, as with carboxyl dihydroxy compounds 201 parts of dihydromethyl propionic acids, as 777 parts of different Buddhists of polyisocyanates Your ketone diisocyanate and as having hydroxyl（Methyl）119 parts of acrylic acid -2- hydroxyl ethyl esters of acrylate and each 0.5 The p methoxy phenol and di-tert-butyl hydroxy toluene of part.60 DEG C are heated to while stirring, are stopped, adding 0.8 part of tin dilaurate Dibutyl tin.Temperature in reaction vessel starts to be heated again if reducing, and persistently stirs at 80 DEG C, uses infrared ray absorbing light Spectrum confirms the absorption spectrum of NCO（2280cm^-1）The then reaction that disappears terminates, and obtains the carbamate of thick liquid Acrylate compounds.Adjusted to nonvolatile component=50 mass % using carbitol acetate.Obtain the acid number of solid constituent The carbamate with carboxyl of 47mgKOH/g, nonvolatile component 50%（Methyl）The resin solution of acrylate compounds. Hereinafter referred to as varnish A-2.

Synthesis example 3

To 2 liters equipped with mixer, thermometer, reflux condenser, dropping funel and nitrogen ingress pipe of removable flask Middle 900 part diethylene glycol dimethyl ethers of the addition as solvent and 21.4 parts of peroxidating 2 ethyl hexanoic acid uncles as polymerization initiator Butyl ester（Japanese grease（Strain）Manufacture, trade name：PERBUTYL O）, it is heated to 90 DEG C.After heating, thereto will with 3 hours 309.9 parts of methacrylic acids, 116.4 parts of methyl methacrylates and 109.8 parts of lactone-modified HEMAs （PLACCEL FM1, DAICEL CHEMICAL INDUSTRIES, LTD. manufactures）With 21.4 parts as the double of polymerization initiator (4- tert-butylcyclohexyls) peroxy dicarbonate（Japanese grease（Strain）Manufacture, trade name：PEROYL TCP）It is added dropwise together and adds Enter, further curing 6 hours, thus obtain copolymer resins containing carboxyl.Additionally, reaction is carried out in a nitrogen atmosphere.

Then, 363.9 parts of acrylic acid 3,4- epoxycyclohexanecarboxylates are added in gained copolymer resins containing carboxyl（DAICEL CHEMICAL INDUSTRIES, LTD. manufacture, trade name：CYCLOMER A200）, as 3.6 parts of diformazans of ring opening catalyst Base benzylamine, as 1.80 parts of hydroquinone monomethyl ethers of polymerization inhibitor, be heated to 100 DEG C, be stirred, so as to carry out epoxy radicals Opening.After 16 hours, obtain solid constituent acid number for 108.9mgKOH/g, weight average molecular weight be 25000, solid into Divide 54% resin solution.Hereinafter referred to as varnish A-3.

Synthesis example 4

1070 parts of o-cresol phenolic epoxy varnish are added in 650 parts of diethylene glycol ether acetate alones（DIC （Strain）Manufacture, EPICLON N-695,95 DEG C of softening point, epoxide equivalent 214, average functionality 7.6）（Glycidol radix（Virtue Fragrant ring sum）：5.0 mole）, 360 parts（5.0 mole）Acrylic acid and 1.5 parts of quinhydrones, are heated to 100 DEG C and stir, uniform molten Solution.Then, 4.3 parts of triphenylphosphines are added, be heated to 110 DEG C reaction 2 hours after, further add 1.6 parts of triphenylphosphines, heat up To 120 DEG C of single step reactions 12 hours of going forward side by side.525 parts of fragrant family hydrocarbon are added in gained reactant liquor（Solvesso 150）、608 Part（4.0 mole）Tetrabydrophthalic anhydride, reacts 4 hours at 110 DEG C.Further, 142.0 parts are added in gained reactant liquor （1.0 mole）GMA, reacts 4 hours at 115 DEG C, obtains solid constituent acid number 77mgKOH/g, consolidates The resin solution of body composition 65%.Hereinafter referred to as varnish R-1.

Synthesis example 5

1070 parts of o-cresol phenolic epoxy varnish are added in 600 parts of diethylene glycol ether acetate alones（DIC （Strain）Manufacture, EPICLON N-695,95 DEG C of softening point, epoxide equivalent 214, average functionality 7.6）（Glycidol radix（Virtue Fragrant ring sum）：5.0 mole）, 360 parts（5.0 mole）Acrylic acid and 1.5 parts of quinhydrones, are heated to 100 DEG C and stir, uniform molten Solution.Then, 4.3 parts of triphenylphosphines are added, be heated to 110 DEG C reaction 2 hours after, be warming up to 120 DEG C of single step reactions 12 of going forward side by side little When.415 parts of fragrant family hydrocarbon are added in gained reactant liquor（Solvesso 150）, 456.0 parts（3.0 mole）Tetrahydrochysene neighbour's benzene two Formic anhydride, reacts 4 hours at 110 DEG C, after cooling, obtains solid constituent acid number 89mgKOH/g, the resin of solid constituent 65% Solution.Hereinafter referred to as varnish R-2.

Synthesis example 6

Add 2200 parts of cresol novolak type epoxy resins（Japanese chemical drug（Strain）Manufacture, EOCN-104S, softening point 92 DEG C, epoxide equivalent 220）, 134 portions of dihydromethyl propionic acid, 648.5 portions of acrylic acid, 4.6 portions of methylnaphthohydroquinones, 1131 portions of carbitol vinegar Acid esters and 484.9 parts of solvent naphthas, are heated to 90 DEG C and stir, and reactant mixture is dissolved.Then, reactant liquor is cooled to 60 DEG C, 13.8 parts of triphenylphosphines are added, be heated to 100 DEG C, reacted about 32 hours, obtain the reaction that acid number is 0.5mgKOH/g Thing.Then, 364.7 parts of tetrabydrophthalic anhydrides, 137.5 parts of carbitol acetates and 58.8 parts of solvent stone brains are added thereto Oil, is heated to 95 DEG C, reacts about 6 hours, cooling, obtain solid constituent acid number 40mgKOH/g, nonvolatile component 65% containing carboxylic The resin solution of base photoresist.Hereinafter referred to as varnish R-3.

Synthesis example 7

By the bisphenol-f type curable type epoxy resin of 400 parts of epoxide equivalents 800,79 DEG C of softening point be dissolved in 925 portions of epichlorohydrins and 462.5 parts of dimethyl sulfoxide (DMSO)s, then under agitation at 70 DEG C with the 81.2 parts of 98.5%NaOH of addition in 100 minutes.After addition, enter one Step is reacted 3 hours at 70 DEG C.Then, most of excessive unreacted epichlorohydrin and dimethyl sulfoxide (DMSO) are distilled remove under reduced pressure Go, the product comprising secondary raw salt and dimethyl sulfoxide (DMSO) is dissolved in 750 parts of methyl iso-butyl ketone (MIBK)s, further add 10 parts 30%NaOH reacts 1 hour at 70 DEG C.After reaction terminates, 2 washings are carried out with 200 parts of water.After water-oil separating, steam from oil reservoir Recovery methyl iso-butyl ketone (MIBK) is evaporated, 370 parts of epoxide equivalents 290, the epoxy resin of 62 DEG C of softening point is obtained（a-1）.Add 2900 parts （10 equivalents）Gained epoxy resin（a-1）, 720 parts（10 equivalents）Acrylic acid, 2.8 parts of methylnaphthohydroquinones, 1950 parts of carbitol acetic acid Ester, is heated to 90 DEG C, and reactant mixture is dissolved in stirring.Then, reactant liquor is cooled to into 60 DEG C, adds 16.7 parts of triphenyls Phosphine, is heated to 100 DEG C, reacts about 32 hours, obtains the reactant that acid number is 1.0mgKOH/g.Then, 786 parts are added thereto （7.86 mole）Succinyl oxide, 423 parts of carbitol acetates, are heated to 95 DEG C, react about 6 hours, obtain solid constituent acid number The resin solution of 100mgKOH/g, solid constituent 65%.Hereinafter referred to as varnish R-4.

Embodiment 1 ~ 13 and comparative example 1 ~ 3

Using the resin solution of above-mentioned synthesis example, in the ratio shown in table 1 together with the various composition shown in table 1 below （Mass parts）Compounding, is pre-mixed with mixer, is then kneaded with triple-roller mill, prepares solder resist photosensitive resin composition Thing.Here, for the decentralization of gained photosensitive polymer combination, according to based on ERICHSEN GmbH ＆ Co.KG manufactures Particle size analyzer（GRIND METER）Granulometry evaluated, be as a result less than 15 μm.

[table 1]

Performance evaluation：

<Optimum exposure>

To copper, thick 18 μm circuit pattern substrate carries out roughened copper surface process（MEC CO., LTD. manufacture MECetchBOND CZ-8100）Afterwards, wash, be dried, then previous embodiment is coated with come whole face by silk screen print method and is compared The light solidifying/heat solidifying resin composition of example, is dried 60 minutes in 80 DEG C of heated air circulation type drying oven.After drying, make With the exposure device of carrying high-pressure sodium lamp across stage exposure meter（Kodak No.2）It is exposed.60 seconds will be carried out Development（30 DEG C, 0.2MPa, 1wt% aqueous sodium carbonate）When light exposure when being 7 sections of the pattern of stage exposure meter that remains make For optimum exposure.

<Developability>

The light solidifying/heat solidifying resin composition of previous embodiment and comparative example is applied to by silk screen print method On full copper base so that dry film thickness is about 25 μm, it is dried 30 minutes in 80 DEG C of heated air circulation type drying oven.After drying, Developed by 1wt% aqueous sodium carbonates, measure dry coating using stopwatch and be removed be to time.

<The maximum development life-span>

The whole face of the composition serigraphy of previous embodiment and comparative example is applied to the copper clad laminate for defining pattern On, it is dried at 80 DEG C, to 80 minutes substrate was taken out every 10 minutes from 20 minutes, naturally cool to room temperature.To this Substrate, is developed 60 seconds, with 30 DEG C of 1wt% aqueous sodium carbonates under conditions of 0.2MPa is sprayed by not remaining residue most Allow drying time as the maximum development life-span greatly.

<Viscosity>

The whole face of the composition serigraphy of previous embodiment and comparative example is applied to the copper clad laminate for defining pattern On, it is dried 30 minutes in 80 DEG C of heated air circulation type drying oven, naturally cool to room temperature.PET egative films are put on the substrate, The HMW-GW20 manufactured with ORC A.B. is pressed at reduced pressure conditions 1 minute, hereafter, when by following benchmark evaluation is peeled off egative film Film coherent condition.

○：When film is peeled off completely without resistance, remain without vestige on film.

△：There is a little resistance when film is peeled off, a little vestige is remained on film.

×：There is resistance when film is peeled off, vestige is substantially remained on film.

Attribute testing：

The whole face of the composition serigraphy of previous embodiment and comparative example is applied to the copper clad laminate for defining pattern On, it is dried 30 minutes at 80 DEG C, naturally cool to room temperature.For the substrate, using the exposure device for being equipped with high-pressure sodium lamp Soldering-resistant pattern is exposed with optimum exposure, is shown under conditions of 0.2MPa is sprayed with 30 DEG C of 1wt% aqueous sodium carbonates Shadow 90 seconds, obtains corrosion-resisting pattern.To the substrate in UV furnace conveyors in accumulated exposure amount 1000mJ/cm²Under conditions of irradiate Ultraviolet, then heats 60 minutes at 150 DEG C and solidifies.For the printed base plate of gained（Evaluate substrate）It is following to evaluate special Property.

<Acid resistance>

Substrate will be evaluated in 10vol%H₂SO₄Impregnate at room temperature in the aqueous solution 30 minutes, with visual infiltration, film are confirmed Dissolution, further by band peel off confirm peel off.

○：Can't see change.

△：Only slight change.

×：Film has expansion or swelling to strip off.

<Alkali resistance>

Substrate will be evaluated in the 10vol%NaOH aqueous solution in room temperature immersion 30 minutes, with it is visual confirm to permeate, film Dissolution, is further peeled off by band and confirms to peel off.

○：Can't see change.

△：Only slight change.

×：Film has expansion or swelling to strip off.

<Resistance to soldering heat performance>

The substrate of evaluating for being coated with rosin series solder flux is immersed in and is redefined in 260 DEG C of solder bath, with modified alcohol Washing solder flux, then with the expansion and stripping of visual valuation resist layer.Judgment standard is as follows.

○：Even if being repeated 3 times the above to impregnate for 10 seconds, stripping is also can't see.

△：When being repeated 3 times 10 seconds dippings of the above, there is a little stripping.

×：Within carrying out 3 times during 10 seconds dippings, resist layer has expansion, peels off.

<The gold-plated property of chemically-resistant>

Bathed using the electroless nickel bath and chemical gilding of commercially available product, under conditions of 5 μm of nickel, 0.05 μm of gold plating carried out, Evaluate resist layer whether there is stripping, whether there is the infiltration of plating by band stripping, then evaluate resist layer whether there is by band stripping Peel off.Judgment standard is as follows.

○：Slight infiltration is confirmed after plating, but is not peeled off after band is peeled off.

△：Slight infiltration is confirmed after plating, band also sees that stripping after peeling off.

×：There is stripping after plating.

<PCT patience>

For the evaluation substrate for defining welding resistance cured coating film, using PCT devices（The HAST of ESPEC Corp. manufactures SYSTEM TPC-412MD）Process 168 hours under conditions of 121 DEG C, saturation, 0.2MPa, evaluate the state of film.Judge base It is accurate as follows.

○：Without expansion, stripping, discoloration, dissolution.

△：There are a little expansion, stripping, discoloration, dissolution.

×：See a large amount of expansions, stripping, discoloration, dissolution.

<Cold-resistant thermal impact>

Make to have and define cloudy, the evaluation substrate of the welding resistance cured coating film of cloudy zero pattern.For gained evaluates substrate, Use cold-hot impact tester（ETAC ENGINEERING CO., LTD. are manufactured）, it was with -55 DEG C/30 minutes ~ 150 DEG C/30 minutes 1 circulation, carries out the resistance test of 1000 circulations.After test, the cured film after by visual observation observation is processed, by following benchmark Evaluate the production of crackle.

○：Crackle generation rate is less than 30%.

△：Crackle generation rate is 30 ~ 50%.

×：Crackle generation rate is more than 50%.

<HAST characteristics>

It is being formed with comb-type electrode（Tooth/spacing=50 micron/50 micron）BT substrates on, formed welding resistance cured coating film, system Judge substrate.Hot and humid groove under the evaluation substrate is put into into 130 DEG C, the atmosphere of humidity 85%, applies 12V voltages, carries out HAST tests in the groove of 168 hours.According to groove interior insulation resistance value of following judgment standard evaluations through 168 hours.

○：More than 10⁸More than Ω.

△：10⁶~10⁸Ω。

×：Less than 10⁶Ω。

The result of aforementioned each evaluation test is shown in table 2 below.

[table 2]

Attribute testing：

The whole face of the composition serigraphy of previous embodiment 13 and comparative example 1 is applied to the Copper Foil base for defining pattern On plate, it is dried 30 minutes at 80 DEG C, naturally cools to room temperature.For the substrate, filled using the exposure for being equipped with high-pressure sodium lamp Put soldering-resistant pattern is exposed with optimum exposure, with 30 DEG C of 1wt% aqueous sodium carbonates under conditions of 0.2MPa is sprayed Development 90 seconds, obtains corrosion-resisting pattern, respectively as embodiment 14 and comparative example 4.In accumulated exposure amount in UV furnace conveyors 1000mJ/cm²Under conditions of to the substrate irradiation ultraviolet radiation, then 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C or 190 DEG C at heating 60 minutes and solidify.For gained printed base plate（Evaluate substrate）, characteristic is evaluated as follows.As a result it is shown in Table 3 and table 4.

<Tg is determined>

The cured film of the size for 3mm × 10mm, with Seiko Instruments Inc.（SII）Manufacture TMA6100 applies the load of 10g while the temperature range with certain programming rate at 0 DEG C -260 DEG C carries out stretching examination Test, calculate extrapolation point to calculate glass transition temperature Tg.

<CTE is determined>

The cured film of the size for 3mm × 10mm, with S eiko Instruments Inc.（SII）Manufacture TMA6100 applies the load of 10g while the temperature range with certain programming rate at 0 DEG C -260 DEG C carries out stretching examination Test.Coefficient of linear thermal expansion CTE is calculated by elongation of the cured film corresponding to temperature.

[table 3]

[table 4]

Embodiment 15 ~ 22 and comparative example 5 ~ 7

By the embodiment 1,3,4,6,7,8,9,11 prepared in the compounding ratio shown in table 1 and each group of comparative example 1,2,3 Compound is diluted with MEK, is applied in PET film, is dried 30 minutes at 80 DEG C, forms thick 20 μm photoresist group Compound layer.Further fit over film thereon to make dry film, respectively as embodiment 15 ~ 22, comparative example 5 ~ 7.

<Dry film is evaluated>

Cover layer is peeled off from the dry film that as above obtains, the thermal laminating films on the copper clad laminate for define pattern, then, Expose under conditions of same with the substrate that the coating characteristic evaluation of previous embodiment is used.After exposure, carrier film is peeled off, with 30 DEG C of 1wt% aqueous sodium carbonates develop 90 seconds under conditions of 0.2MPa is sprayed, and obtain corrosion-resisting pattern.In UV furnace conveyors In with accumulated exposure amount 1000mJ/cm²Condition to the substrate irradiation ultraviolet radiation, then heat at 150 DEG C 60 minutes and solidify. For the test substrate that gained has cured film, the evaluation examination of each characteristic is carried out with aforesaid test method and evaluation method Test.As a result it is shown in table 5.

[table 5]

<Dry film is evaluated>

Using previous embodiment 1 and the composition of comparative example 1, cover layer is peeled off from the dry film for as above obtaining, defined Thermal laminating films on the copper clad laminate of pattern, then, the substrate used in the coating characteristic evaluation with previous embodiment is same Under conditions of expose.After exposure, carrier film is peeled off, with 30 DEG C of 1wt% aqueous sodium carbonates under conditions of 0.2MPa is sprayed Development 90 seconds, obtains corrosion-resisting pattern, respectively as embodiment 23 and comparative example 8.With accumulated exposure amount in UV furnace conveyors 1000mJ/cm²Condition to the substrate irradiation ultraviolet radiation, then at 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C Or heating solidifies for 60 minutes at 190 DEG C.For the test substrate that gained has cured film, with aforesaid test method and evaluation Method carries out the evaluation test of each characteristic.As a result table 6 and table 7 are shown in.

[table 6]

[table 7]

Result by shown in aforementioned table 6 and table 7 is it will be evident that the light solidifying/heat solidifying resin composition of the present invention As the PCT patience, cold-resistant thermal impact, HAS T characteristics that have concurrently required for semiconductor-sealing-purpose solder mask（Electrical characteristics）Light Curability hot curing resin composition is useful.

Industrial applicability

By using the present invention light solidifying/heat solidifying resin composition, can be formed PCT patience, HAST patience, The excellent cured films such as the gold-plated property of chemically-resistant, heat resistance, therefore printed circuit board (PCB), flexible circuit can be suitably used to form The solder mask of plate etc., particularly semiconductor-sealing-purpose solder mask.

Claims (6)

1. the light solidifying/heat solidifying resin composition that a kind of energy of semiconductor-sealing-purpose is developed by aqueous alkali, its feature It is that it contains：

Containing carboxy resin, wherein exclude with epoxy resin as initiation material containing carboxy resin；

Photoepolymerizationinitiater initiater；With

Naphthalene nucleus is the epoxy resin containing naphthalene nucleus of planar structure,

It is described containing carboxy resin for following (2)～(5) any at least one：

(2) make the monocarboxylic acid containing unsaturated group with, make the compound and ring-type carbon in 1 molecule with more than 2 phenolic hydroxyl group Product obtained from ester compound reaction is reacted, and is made obtained from multi-anhydride and gained reaction Photoresist containing carboxyl；

(3) end of polyurethane resin and the carboxylic polyurethane resin in end of anhydride reaction, the polyurethane tree are made Fat is obtained from the sudden reaction by diisocyanate cpd and polyol compound；

(4) carboxyl is contained obtained from the sudden reaction by diisocyanate with compound containing carboxylic diol and diol compound The chemical combination in 1 molecule with 1 hydroxyl and more than 1 acryloyl group or methylacryloyl is added in the synthesis of polyurethane resin Thing, terminal acrylic is acylated or polyurethane resin containing carboxyl obtained from metering system acylation；

(5) carboxyl is contained obtained from the sudden reaction by diisocyanate with compound containing carboxylic diol and diol compound Add in the synthesis of polyurethane resin and have in 1 molecule 1 NCO and more than 1 acryloyl group or methylacryloyl Compound, by terminal acrylic be acylated or metering system be acylated obtained from polyurethane resin containing carboxyl.

2. light solidifying/heat solidifying resin composition according to claim 1, it is characterised in that described containing carboxy resin With phenolic resin as initiation material.

3. light solidifying/heat solidifying resin composition according to claim 1, it is characterised in that described containing carboxy resin With photonasty group.

4. a kind of dry film of Photosetting and thermosetting, it is by the photo-curable heat any one of the claims 1 to 3 Hardening resin composition is coated with a carrier film and is dried and obtains.

5. a kind of solidfied material, it is to the Photosetting and thermosetting resin combination any one of the claims 1 to 3 Thing or to by the light solidifying/heat solidifying resin composition be coated on carrier and be dried obtained from dry film carry out photocuring And obtain.

6. a kind of printed circuit board (PCB), it has cured film, and the cured film is by arbitrary in the claims 1 to 3 Described in light solidifying/heat solidifying resin composition or to the light solidifying/heat solidifying resin composition is coated on into load After dry film irradiates active energy beam so as to be light-cured into pattern-like on body film and obtained from drying, carry out heat cure and obtain Arrive.